EP2905786A1 - Scintillator panel and method for producing scintillator panel - Google Patents
Scintillator panel and method for producing scintillator panel Download PDFInfo
- Publication number
- EP2905786A1 EP2905786A1 EP13843088.9A EP13843088A EP2905786A1 EP 2905786 A1 EP2905786 A1 EP 2905786A1 EP 13843088 A EP13843088 A EP 13843088A EP 2905786 A1 EP2905786 A1 EP 2905786A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- barrier rib
- scintillator panel
- mass
- melting
- photosensitive paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000004888 barrier function Effects 0.000 claims abstract description 234
- 239000011521 glass Substances 0.000 claims abstract description 105
- 239000000758 substrate Substances 0.000 claims abstract description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 17
- 238000010304 firing Methods 0.000 claims description 55
- 239000011248 coating agent Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 49
- 238000011161 development Methods 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 description 80
- 239000000843 powder Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 230000007423 decrease Effects 0.000 description 20
- 230000007547 defect Effects 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 239000011295 pitch Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000006096 absorbing agent Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 230000005855 radiation Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 238000007650 screen-printing Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 7
- -1 cesium iodide (CsI) Chemical compound 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 235000019325 ethyl cellulose Nutrition 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000004034 viscosity adjusting agent Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 150000003476 thallium compounds Chemical class 0.000 description 2
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- CNGTXGHYZBQUQS-UHFFFAOYSA-N ((1-(2-methoxyethoxy)ethoxy)methyl)benzene Chemical compound COCCOC(C)OCC1=CC=CC=C1 CNGTXGHYZBQUQS-UHFFFAOYSA-N 0.000 description 1
- MLIWQXBKMZNZNF-PWDIZTEBSA-N (2e,6e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)C\C1=C/C1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-PWDIZTEBSA-N 0.000 description 1
- UZNOMHUYXSAUPB-UNZYHPAISA-N (2e,6e)-2,6-bis[(4-azidophenyl)methylidene]cyclohexan-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1\C=C(/CCC\1)C(=O)C/1=C/C1=CC=C(N=[N+]=[N-])C=C1 UZNOMHUYXSAUPB-UNZYHPAISA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 1
- SFSLTRCPISPSKB-UHFFFAOYSA-N 10-methylideneanthracen-9-one Chemical compound C1=CC=C2C(=C)C3=CC=CC=C3C(=O)C2=C1 SFSLTRCPISPSKB-UHFFFAOYSA-N 0.000 description 1
- PLGAYGHFBSTWCA-UHFFFAOYSA-N 10-phenylsulfanylacridin-9-one Chemical compound C1(=CC=CC=C1)SN1C=2C=CC=CC2C(C2=CC=CC=C12)=O PLGAYGHFBSTWCA-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- VSXIZXFGQGKZQG-UHFFFAOYSA-N 2-cyano-3,3-diphenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)O)C1=CC=CC=C1 VSXIZXFGQGKZQG-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- UVNIWYMQSYQAIS-UHFFFAOYSA-N 3-(4-azidophenyl)-1-phenylprop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=CC(=O)C1=CC=CC=C1 UVNIWYMQSYQAIS-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- BMVWCPGVLSILMU-UHFFFAOYSA-N 5,6-dihydrodibenzo[2,1-b:2',1'-f][7]annulen-11-one Chemical compound C1CC2=CC=CC=C2C(=O)C2=CC=CC=C21 BMVWCPGVLSILMU-UHFFFAOYSA-N 0.000 description 1
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004755 Cerium(III) bromide Inorganic materials 0.000 description 1
- 229910008069 Cerium(III) iodide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910016859 Lanthanum iodide Inorganic materials 0.000 description 1
- 229910014323 Lanthanum(III) bromide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- BRHJUILQKFBMTL-UHFFFAOYSA-N [4,4-bis(dimethylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound C1=CC(N(C)C)(N(C)C)CC=C1C(=O)C1=CC=CC=C1 BRHJUILQKFBMTL-UHFFFAOYSA-N 0.000 description 1
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 238000002438 flame photometric detection Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- DQZARQCHJNPXQP-UHFFFAOYSA-N gadolinium;sulfur monoxide Chemical compound [Gd].S=O DQZARQCHJNPXQP-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- DASJFYAPNPUBGG-UHFFFAOYSA-N naphthalene-1-sulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1 DASJFYAPNPUBGG-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VHXJRLYFEJAIAM-UHFFFAOYSA-N quinoline-2-sulfonyl chloride Chemical compound C1=CC=CC2=NC(S(=O)(=O)Cl)=CC=C21 VHXJRLYFEJAIAM-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002601 radiography Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- BOUDEKXATYHWHY-UHFFFAOYSA-K thallium(3+);trifluoride Chemical compound F[Tl](F)F BOUDEKXATYHWHY-UHFFFAOYSA-K 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/2002—Optical details, e.g. reflecting or diffusing layers
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/2018—Scintillation-photodiode combinations
- G01T1/20183—Arrangements for preventing or correcting crosstalk, e.g. optical or electrical arrangements for correcting crosstalk
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14658—X-ray, gamma-ray or corpuscular radiation imagers
- H01L27/14663—Indirect radiation imagers, e.g. using luminescent members
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/08—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with a binder in the phosphor layer
Definitions
- the present invention relates to a scintillator panel which constitutes a radiation detector that is used for a medical diagnostic apparatus, a nondestructive inspection instrument and the like.
- X-ray images using films have been widely used heretofore in medical settings.
- the X-ray image using a film provides analog image information
- digital radiation detectors such as computed radiography (CR) and flat panel radiation detectors (flat panel detectors: FPDs) have been developed.
- a scintillator panel is used for converting a radiation into visible light.
- the scintillator panel contains,an X-ray phosphor such as cesium iodide (CsI), the X-ray phosphor emits visible light in response to an applied X-ray, and the emitted light is converted into an electric signal by a TFT (thin film transistor) or a CCD (charge-coupled device) to thereby convert X-ray information into digital image information.
- the FPD has a problem of low S/N ratio. This is attributable to scattering of visible light by the X-ray phosphor itself when the X-ray phosphor emits light, etc.
- Patent Documents 1 to 4 For reducing influences of the scattering of light, methods of filling an X-ray phosphor in cells divided by a barrier rib have been proposed (Patent Documents 1 to 4).
- the shape of the barrier rib varies depending on a pitch, but the width is approximately 5 to 40 ⁇ m, and the height is approximately 100 to 800 ⁇ m.
- the method which has been heretofore used as a method for forming the barrier rib is a method of etching a silicon wafer, or a method in which a glass paste, a mixture of a pigment or a ceramic powder and a low-melting-point glass powder, is pattern-printed in multiple layers using a screen printing method, and then fired to form a barrier rib.
- the size of a scintillator panel that can be formed is restricted by the size of a silicon wafer, and a scintillator panel having a large size of, for example, 500 mm square cannot be obtained.
- a plurality of small-size panels should be arranged for making a large-size panel, but production of a scintillator panel in this way is difficult in terms of accuracy, and it is difficult to prepare a large-area scintillator panel.
- a definite barrier rib width is required for enhancing the strength of a barrier rib in order to prevent destructive defects of the barrier rib.
- a scintillator panel obtained in this method has the disadvantage that the amount of an X-ray phosphor is so small that the luminescence is reduced, and luminous unevenness occurs. This disadvantage makes it difficult to photograph sharp images in photographing in a low radiation dose.
- a technique for processing a barrier rib which is capable of processing the barrier rib with high accuracy over a large area and narrowing the width of the barrier rib, and a technique for preventing visible light, which is emitted by an X-ray phosphor, from being leaked to outside are required.
- An object of the present invention is to solve the above-described disadvantages and provide a scintillator panel which is provided with a narrow barrier rib with high accuracy in a large area, has high luminous efficiency, and provides sharp images.
- a barrier rib having a high strength can be formed with high accuracy in a large area, and visible slight emitted by a phosphor can be efficiently utilized, so that there can be provided a scintillator panel which has a large size and provides sharp images, and a method for manufacturing the scintillator panel.
- Fig. 7 is a sectional view schematically showing the configuration of a radiation detector including a scintillator panel of the present invention.
- Fig. 8 is a perspective view schematically showing the configuration of the scintillator panel of the present invention.
- a radiation detector 1 includes a scintillator panel 2, an output substrate 3 and a power supply portion 12.
- the scintillator panel 2 includes a scintillator layer 7 including a phosphor, and absorbs energy of an incident radiation such as an X-ray to emit an electromagnetic wave having a wavelength ranging from 300 to 800 nm, i.e. an electromagnetic wave (light) which ranges from ultraviolet light to infrared light with visible light at the center.
- the scintillator panel 2 includes a substrate 4, a grid-like barrier rib 6 formed on the substrate and intended for dividing cells, and a scintillator layer 7 including a phosphor filled in a cell formed by the barrier rib.
- a reflecting film 13 is formed on the barrier rib 6 and the substrate 4. Owing to the reflecting film 13, visible light emitted by the phosphor can be reflected without passing through the barrier rib 6, and resultantly light emitted at the scintillator layer 7 can be made to reach a photoelectric conversion layer 9 on the output substrate 3 efficiently.
- the output substrate 3 has the photoelectric conversion layer 9 in which pixels including photosensors and TFT are two-dimensionally formed, and an output layer 10 on a substrate 11.
- the radiation detector 1 is formed. Light emitted at the scintillator layer 7 reaches the photoelectric conversion layer 9, undergoes photoelectric conversion at the photoelectric conversion layer 9, and generates output.
- each cell is divided by a barrier rib, and therefore when the size and pitch of pixels of a photoelectric conversion element arranged in a grid-like shape are made coincident with the size and pitch of cells of the scintillator panel, scattered light can be prevented from reaching a neighboring cell even though light is scattered by a phosphor. In this way, blurring of images resulting from light scattering can be reduced, so that high-accuracy photographing is possible.
- the barrier rib that forms the scintillator panel of the present invention is required to satisfy the following requirement: a value obtained by dividing Lt by Lh is 0.45 to 1 and a value obtained by dividing Lb by Lh is 1 to 3 where Lt is a top width of the barrier rib, Lh is a half-value width of the barrier rib, and Lb is a bottom width of the barrier rib.
- the value obtained by dividing Lt by Lh is preferably 0.6 to 1, more preferably 0.8 to 1, further preferably 0.8 to 0.95.
- the value obtained by dividing Lb by Lh is preferably 1 to 2, more preferably 1 to 1.5, further preferably 1.3 to 1.5.
- Lt, Lh and Lb in the barrier rib of the first aspect are shown in Fig. 1 .
- Lh refers to a line width of a portion at a height of 50 from the bottom surface of the barrier rib where the height of the barrier rib is 100 (hereinafter, referred to as "barrier rib central portion") at a cross section perpendicular to the longitudinal direction in the barrier rib.
- Lt/Lh is more than 1, constriction occurs at the periphery of the central portion of the barrier rib, so that filling amount of the phosphor to the pitch of the barrier rib decreases, and an opening for extracting light emitted by the phosphor is narrowed, leading to a decrease in luminance. Besides, nonuniformity such as coating unevenness and thickness unevenness occurs at the time of filling the phosphor.
- the top of the barrier rib becomes extremely narrow, causing a shortage of strength for sustaining a pressure applied at the time of bonding the scintillator panel to a light detection substrate, so that the top of the barrier rib may be easily collapsed, or the barrier rib may be cut at some midpoint, leading to occurrence of breakage.
- Lb/Lh is less than 1, the strength of the barrier rib decreases, so that falling, breakage or torsion of the barrier rib occurs. On the other hand, if Lb/Lh is more than 3, the filling amount of the phosphor decreases, so that the luminance decreases.
- the shape of the barrier rib described above can be controlled by changing various conditions described later.
- a 90%-height width (L90) in place of Lt or a 10%-height width (L10) in place of Lb can be used.
- L90 90%-height width
- L10 10%-height width
- a value obtained by dividing L90 by Lh be 0.45 to 1
- a value obtained by dividing L10 by Lh be 1 to 3.
- the value obtained by dividing L90 by Lh is preferably 0.8 to 1
- the value obtained by dividing L10 by Lh is preferably 1 to 1.5.
- L90, Lh and L10 in the barrier rib of the second aspect are shown in Fig. 2 .
- L90 refers to a line width of a portion at a height of 90 from the bottom surface of the barrier rib where the height of the barrier rib is 100 at a cross section perpendicular to the longitudinal direction in the barrier rib.
- L10 refers to a line width of a portion at a height of 10 from the bottom surface of the barrier rib where the height of the barrier rib is 100 at a cross section perpendicular to the longitudinal direction in the barrier rib.
- Line widths of the barrier rib such as Lt, Lb, L90, L10 and Lh, can be each calculated by repeatedly measuring 25 random spots on the formed barrier rib with a scanning electron microscope (for example, "S-4800” manufactured by Hitachi, Ltd.), and determining an average thereof.
- a scanning electron microscope for example, "S-4800” manufactured by Hitachi, Ltd.
- the measurement with a scanning electron microscope can be made in the following manner.
- the barrier rib is cut at right angles to the stripe direction of the barrier rib, i.e. the longitudinal direction, so that the cross section of the barrier rib is as shown in Fig. 1 etc., and the cross section is processed to a size available for observation with a scanning electron microscope.
- a magnification a magnification is selected so that the visual field includes 2 to 5 barrier ribs.
- the pitch of the barrier rib is 160 ⁇ m
- a magnification of 200 to 300 may be selected.
- the reduced scale can be calibrated with a standard sample having a size comparable to the line width of the barrier rib, followed by taking a picture, and calculating a line width from the reduced scale.
- the line S that connects the end of the central portion of the barrier rib to the end of the bottom surface of the barrier rib at a cross section perpendicular to the longitudinal direction in the barrier rib is not limited to a straight line as shown in Fig. 1 , and may be a curved line having a curvature radius R as shown in Fig. 4 .
- the line S is preferably a curved line because even when the value obtained by dividing Lb by Lh increases, a wide phosphor filling space can be secured, so that the luminance does not decrease.
- the curvature radius R of the line S is preferably Lh or greater.
- Lh is preferably 5 to 40 ⁇ m. If Lh is more than 40 ⁇ m, the opening ratio decreases, so that a sufficient luminance is not obtained. On the other hand, if Lh is less than 5 ⁇ m, the barrier rib has an insufficient strength, resulting in occurrence of falling or torsion of the barrier rib.
- the pitch of the barrier rib is preferably 30 to 300 ⁇ m, more preferably 50 to 240 ⁇ m.
- the height of the barrier rib is preferably 50 to 3000 ⁇ m, more preferably 100 to 800 ⁇ m. If the height of the barrier rib is less than'50 ⁇ m, sufficient luminance is not obtained. On the other hand, if the height of the barrier rib is more than 3000 ⁇ m, luminous efficiency decreases.
- the barrier rib has a shape in which Lh is 5 to 30 ⁇ m and H is 100 to 500 ⁇ m when P is 50 to 120 ⁇ m.
- Lh is 10 to 40 ⁇ m and H is 200 to 800 ⁇ m when P is 120 to 240 ⁇ m.
- the material of the substrate to be used for the scintillator panel of the present invention is preferably a material pervious to radiations, and various kinds of glasses, polymer materials, metals and the like can be used.
- a glass plate containing a glass such as quartz, borosilicate glass or chemically reinforced glass
- a ceramic substrate containing a ceramic such as sapphire, silicon nitride, silicon carbide
- a polymer film (plastic film) such as a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, a triacetate film, a polycarbonate film or a carbon fiber reinforced resin sheet
- a metal sheet such as an aluminum sheet, an iron sheet or a copper sheet
- a barrier rib is formed on the substrate.
- the barrier rib is required to be formed of a material which is mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide in terms of durability, heat resistance and high-definition processing.
- the material which is mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide has a proper refractive index and a softening temperature, and is suitable for forming a narrow barrier rib in a large area and with high accuracy.
- the low-melting-point glass refers to a glass having a softening temperature of 700°C or lower.
- a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide means that a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide constitutes 50 to 100% by mass of a material that forms the barrier rib.
- a method for manufacturing the scintillator panel of the present invention includes: a step of forming a photosensitive paste coating film by applying onto a substrate a photosensitive paste which contains a low-melting-point glass and a photosensitive organic component; an exposure step of exposing the obtained photosensitive paste coating film to light in a predetermined pattern; a development step of dissolving and removing a part of the exposed photosensitive paste coating film which is soluble in a developer; a firing step of heating the photosensitive paste coating film pattern after development to a firing temperature of 500 to 700°C to remove the organic component and soften and sinter the low-melting-point glass and thereby forming a barrier rib; forming a metallic reflecting film at a temperature lower than the firing temperature using a vacuum film formation method; and a step of filling a phosphor.
- a necessary part of the photosensitive paste coating film is photocured, or an unnecessary part of the photosensitive paste coating film is photodecomposed by exposure to add a contrast of dissolution of the photosensitive paste coating film in a developer.
- the development step an unnecessary part of the exposed photosensitive paste coating film is removed with a developer, so that a photosensitive paste coating film pattern in which only a necessary part of the coating film remains is obtained.
- the obtained photosensitive paste coating film pattern is fired at a temperature of 500 to 700°C, preferably 500 to 650°C, whereby the organic component is decomposed and distilled away, and the low-melting-point glass is softened and sintered to form a barrier rib containing a low-melting-point glass.
- the firing temperature is preferably 500°C or higher. If the firing temperature is higher than 700°C, deformation of the substrate increases when a general glass substrate is used as the substrate, and therefore the firing temperature is preferably 700°C or lower.
- the method of the present invention is capable of processing with high accuracy as compared to a processing method in which a glass paste is printed by laminating by a multi-layer screen printing and then fired.
- the photosensitive paste for use in the present invention is formed of an organic component containing a photosensitive organic component, and an inorganic powder containing a low-melting-point glass containing 2 to 20% by-mass of an alkali metal oxide.
- the organic component is required in a definite amount for forming a photosensitive paste coating film pattern before firing, but if the amount of the organic component is excessively large, the amount of substances removed in the firing step increases, so that the shrinkage rate after firing becomes large, and therefore pattern defects easily occur in the firing step.
- the content of the inorganic powder in the photosensitive paste is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
- the content of the inorganic powder being less than 30% by mass is not preferable because the shrinkage rate during firing increases to cause breakage and peeling of the barrier rib. Further, pattern thickening and remaining of a film during development easily occur, and Lb/Lh easily becomes greater than 3.
- the content of less than 30% by mass is not preferable.
- the content of the inorganic powder is more than 80% by mass, the amount of the photosensitive organic component decreases, so that the photosensitive paste coating film is not photocured to the bottom in the exposure step.
- Lt/Lh easily becomes greater than 1, and Lb/Lh easily becomes smaller than 1. Therefore, the content of more than 80% by mass is not preferable.
- the content of the low-melting-point glass is preferably 50 to 100% by mass based on the total of the inorganic powder.
- the content of the low-melting-point glass being less than 50% by mass with respect to the inorganic powder is not preferable because sintering does not properly proceed in the firing step, and therefore the strength of the barrier rib obtained decreases.
- a low-melting-point glass containing a low-melting-point glass having a softening temperature of 480°C or higher it is preferable to use a low-melting-point glass containing a low-melting-point glass having a softening temperature of 480°C or higher. If the softening temperature is lower than 480°C, the low-melting-point glass is softened before the organic component is sufficiently removed during firing, so that residues of the organic component are captured in the glass. In this case, the organic component may be gradually released later to deteriorate product quality. Further, residues of the organic component captured in the glass become a cause of coloring of the glass.
- the organic component can be completely removed.
- the firing temperature be 500 to 700°C. Since the firing temperature is preferably 500 to 650°C, the softening temperature of the low-melting-point glass is preferably 480 to 680°C, more preferably 480 to 620°C.
- the softening temperature is determined by extrapolating a heat absorption completion temperature at an endothermic peak by a tangent method from a DTA curve obtained by measuring a sample using a differential thermal analyzer (DTA, "Differential Type Differential Thermal Balance TG8120" manufactured by Rigaku Corporation). Specifically, an inorganic powder as a measurement sample is measured by elevating the temperature at 20°C/minute from room temperature with an alumina powder as a standard sample using a differential thermal analyzer, thereby obtaining a DTA curve.
- a softening point Ts determined by extrapolating a heat absorption completion temperature at an endothermic peak by a tangent method from the obtained DTA curve is defined as a softening temperature.
- a metal oxide selected from the group consisting of lead oxide, bismuth oxide, zinc oxide and alkali metal oxides, which are materials effective for lowering the melting point of glass can be used.
- the alkali metal refers to lithium, sodium, potassium, rubidium and cesium, but the alkali metal oxide for use in the present invention refers to a metal oxide selected from the group consisting of lithium oxide, sodium oxide and potassium oxide.
- the content X of an alkali metal oxide (M 2 O) in the low-melting-point glass be in a range of 2 to 20% by mass. If the content of the alkali metal oxide is less than 2% by mass, the softening temperature becomes high, and therefore it is necessary to perform the firing step at a high temperature. Accordingly, when a glass substrate'is used as the substrate, it is likely that the scintillator panel obtained is distorted or defects occur in the barrier rib due to deformation of the substrate in the firing step, and therefore the content of less than 2% by mass is not suitable. If the content of the alkali metal oxide is more than 20% by mass, the viscosity of glass decreases too much in the firing step. Accordingly, the shape of the barrier rib obtained is easily distorted. Further, the porosity of the barrier rib obtained becomes excessively small, leading to a decrease in light emission luminance of the scintillator panel obtained.
- M 2 O alkali metal oxide
- the viscosity of glass at a high temperature it is preferable to add 3 to 10% by mass of zinc oxide in addition to the alkali metal oxide for adjusting the viscosity of glass at a high temperature. If the content of zinc oxide is less than 3% by mass, the viscosity of glass at a high temperature becomes high, and addition of zinc oxide in an amount of more than 10% by mass tends to increase the cost of glass.
- the stability, crystallinity, transparency, refractive index, thermal expansion characteristic or the like of the low-melting-point glass can be controlled.
- the composition range shown below is preferable because a low-melting-point glass having a viscosity characteristic suitable for the present invention can be prepared.
- the alkali earth metal refers to one or more metal selected from the group consisting of magnesium, calcium, barium and strontium.
- the particle diameter of inorganic particles containing a low-melting-point glass can be evaluated using a particle size distribution analyzer ("MT 3300" manufactured by NIKKISO CO., LTD.).
- MT 3300 manufactured by NIKKISO CO., LTD.
- an inorganic powder is charged in a sample chamber filled with water, and subjected to an ultrasonic treatment for 300 seconds, followed by performing a measurement.
- the 50% volume average particle diameter (D50) of the low-melting-point glass is preferably 1.0 to 4.0 ⁇ m. If D50 is less than 1.0 ⁇ m, agglomeration of particles becomes strong, so that it becomes difficult to achieve-uniform dispersibility, leading to unstable fluidity of a paste. In this case, thickness uniformity when a paste is applied is deteriorated. If D50 is more than 4.0 ⁇ m, the surface unevenness of a sintered body obtained increases, so that a pattern tends to be broken in a subsequent step.
- the photosensitive paste for use in the present invention may contain as a filler a high-melting-point glass that is not softened at 700°C, or ceramic particles such as those of silicon oxide, aluminum oxide, titanium oxide or zirconium oxide in addition to the above-described low-melting-point glass.
- the filler when used together with the low-melting-point glass, has an effect of controlling the shrinkage rate after firing of a paste composition and retaining the shape of the barrier rib formed.
- the ratio of the filler to the total of the inorganic powder is more than 50% by mass, sintering of the low-melting-point glass is hindered to cause a problem such as a reduction in strength of the barrier rib, and therefore the ratio of more than 50% by mass is not preferable.
- the filler has an average particle diameter of 0.5 to 4.0 ⁇ m for the same reason as that described for the low-melting-point glass.
- the average refractive index n1 of the low-melting-point glass and the average refractive index n2 of the photosensitive organic component satisfy preferably -0.1 ⁇ n1 - n2 ⁇ 0.1, more preferably -0.01 ⁇ n1 - n2 ⁇ 0.01, further preferably -0.005 ⁇ n1 - n2 ⁇ 0.005.
- n1 - n2 ⁇ -0.01 or n1 - n2 > 0.01 light scattering easily occurs at the interface between the low-melting-point glass and the photosensitive organic component in the exposure step.
- the exposure amount is small in the exposure step, light does not reach the bottom of the photosensitive paste coating film, and therefore Lt/Lh easily becomes greater than 1 and Lb/Lh easily becomes smaller than 1. Therefore, the relationship of n1 - n2 ⁇ -0.01 or n1 - n2 > 0.01 is not preferable.
- increasing the exposure amount is not preferable because the photosensitive paste coating film is cured by scattered light due to increased light scattering, so that Lt/Lh easily becomes smaller than 0.45 and Lb/Lh easily becomes greater than 3.
- a low-melting-point glass having both a preferable heat characteristic and a preferable average refractive index can be obtained.
- the refractive index of the low-melting-point glass can be measured using a Becke line detection method.
- a refractive index at 25°C and at a wavelength of 436 nm (g-line) was defined as the refractive index of the low-melting-point glass in the present invention.
- the average refractive index of the photosensitive organic component can be determined by measuring a coating film composed of a photosensitive organic component by ellipsometry.
- a refractive index at 25°C and at a wavelength of 436 nm (g-line) was defined as the average refractive index of the photosensitive organic component.
- the photosensitive paste for use in the present invention includes a photosensitive organic component as an organic component, it can be pattern-processed by the photosensitive paste method described above.
- a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer, a photo-polymerization initiator or the like as the photosensitive organic component, reactivity can be controlled.
- the photosensitivity in the photosensitive monomer, the photosensitive oligomer and the photosensitive polymer means that when the paste is irradiated with active light rays, the photosensitive monomer, the photosensitive oligomer or the photosensitive polymer undergoes a reaction of photo-crosslinking, photo-polymerization or the like to change the chemical structure.
- the photosensitive monomer is a compound having an active carbon-carbon double bond, and examples thereof include monofunctional compounds and polyfunctional compounds having a vinyl group, an acryloyl group, a methacryloyl group or an acrylamide group as a functional group.
- the photosensitive organic component contains 10 to 80% by mass of a compound selected from the group consisting of polyfunctional acrylate compounds and polyfunctional methacrylate compounds from the viewpoint of increasing the crosslinking density during curing by a photoreaction to improve pattern formability.
- the polyfunctional acrylate compounds and polyfunctional methacrylate compounds a variety of kinds of compounds have been developed, and an appropriate one can be selected from those compounds in consideration of reactivity, a refractive index and the like.
- the photosensitive oligomer or the photosensitive polymer an oligomer or polymer having an active carbon-carbon unsaturated double bond is preferably used.
- the photosensitive oligomer or the photosensitive polymer is obtained by, for example, copolymerizing a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or an acid anhydride thereof, and a monomer such as a methacrylic acid ester, an acrylic acid ester, styrene, acrylonitrile, vinyl acetate or 2-hydroxy acrylate.
- a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or an acid anhydride thereof
- a monomer such as a methacrylic acid ester, an acrylic acid ester, styrene, acrylon
- a method for introducing an active carbon-carbon unsaturated double bond into an oligomer or a polymer a method can be used in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or acryl chloride, or a carboxylic acid such as maleic acid is reacted with a mercapto group, an amino group, a hydroxyl group or a carboxyl group in an oligomer or a polymer, etc.
- a photosensitive paste insusceptible to pattern defects in the firing step can be obtained.
- pattern defects are suppressed because rapid shrinkage is hard to occur in the process of sintering of a glass in the later stage of the firing step due to use of a low-melting-point glass as the glass.
- a compound having a urethane structure is used for the organic component, stress is relaxed in the process of decomposition and distillation of the organic component in the early stage of the firing step, so that pattern defects are hard to occur. Owing to both the effects described above, pattern defects can be suppressed over a wide temperature range.
- the photo-polymerization initiator is a compound which generates radicals when irradiated with an active light ray.
- Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyl diphenyl ketone, dibenzyl ketone, fluorenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquino
- the content of the photo-polymerization initiator is not limited, but is preferably in a range of 0.05 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the photosensitive component. If the amount of the photo-polymerization initiator decreases, the photosensitivity decreases, and the barrier rib is thinned. If the amount of the photo-polymerization initiator increases, the barrier rib is thickened.
- the photosensitive paste contains an ultraviolet ray absorber.
- an ultraviolet ray absorber By adding an ultraviolet ray absorber, a barrier rib having a high aspect ratio, a high definition and a high resolution can be obtained.
- the ultraviolet ray absorber is a compound having a high ultraviolet ray absorption effect.
- the ultraviolet ray absorber is preferably an organic dye, and particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used.
- azo-based dyes aminoketone-based dyes, xanthene-based dyes, quinoline-based dyes, aminoketone-based dyes, anthraquinone-based dyes, benzophenone-based dyes, diphenylcyanoacrylate-based dyes, triazine-based dyes, p-aminobenzoic acid-based dyes and the like can be used.
- the organic-based dye does not remain in the barrier rib after firing, and is therefore preferable.
- azo-based and benzophenone-based dyes are preferable.
- the amount of the ultraviolet ray absorber is not limited, but is preferably in a range of 0.1 to 60% by mass, more preferably 0.1 to 30% by mass with respect to the photosensitive component.
- the relationship between the amount of the ultraviolet ray absorber and the shape of the barrier rib obtained also depends on an absorption wavelength of the ultraviolet ray absorber. For example, in the case of an ultraviolet ray absorber having a high UV absorption coefficient in a range of 350 to 450 nm, Lt/Lh easily decreases and Lb/Lh easily increases if the amount of the ultraviolet ray absorber is large. Conversely, if the amount of the ultraviolet ray absorber is small, Lt/Lh easily increases and Lb/Lh easily decreases.
- the photosensitive paste may contain as a binder a copolymer having a carboxyl group.
- the copolymer having a carboxyl group is obtained by, for example, selecting a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or an acid anhydride thereof and other monomers such as a methacrylic acid ester, an acrylic acid ester, styrene, acrylonitrile, vinyl acetate or 2-hydroxy acrylate, and copolymerizing the monomers using an initiator such as azobisisobutyronitrile.
- a copolymer having an acrylic acid ester or a methacrylic acid ester and an acrylic acid or a methacrylic acid as copolymerization components is preferably used because the thermal decomposition temperature during firing is low.
- the photosensitive paste is a paste excellent in solubility in an alkali aqueous solution when it contains a copolymer having a carboxyl group.
- the acid value of the copolymer having a carboxyl group is preferably 50 to 150 mg KOH/g. When the acid value is 150 mg KOH/g or less, the allowable range of development can be widened. When the acid value is 50 mg KOH/g or more, solubility of an unexposed part in a developer is not reduced. Therefore, it is not necessary to increase the concentration of a developer, and peeling of an exposed part is prevented, so that a high-definition pattern can be obtained.
- the copolymer having a carboxyl group has an ethylenically unsaturated group on a side chain.
- the ethylenically unsaturated group include an acryl group, a methacryl group, a vinyl group and an allyl group.
- the photosensitive paste is prepared by adding an organic solvent and a binder as required to a low-melting-point glass and a photosensitive organic component containing a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer, a photo-polymerization initiator or the like, and compounding various components so as to achieve a predetermined composition, followed by uniformly mixing and dispersing the mixture using a three-roll roller or a kneader.
- the viscosity of the photosensitive paste can be appropriately adjusted by the added ratios of an inorganic powder, a thickener, an organic solvent, a polymerization inhibitor, a plasticizer, a precipitation preventive agent and so on, and is preferably in a range of 2 to 200 Pa•s.
- a viscosity of 2 to 5 Pa•s is preferable.
- a viscosity of 50 to 200 Pa•s is preferable.
- a blade coater method, a die coater method or the like a viscosity of 10 to 50 Pa•s is preferable.
- a barrier rib By applying the photosensitive paste thus obtained onto the substrate, forming a desired pattern by a photolithography method and performing firing, a barrier rib can be formed.
- An example of manufacturing a barrier rib by the photolithography method using the above-described photosensitive paste will be described, but the present invention is not limited thereto.
- the photosensitive paste is applied onto the whole or part of the substrate surface to form a photosensitive paste coating film.
- a screen printing method or a method using a bar coater, a roll coater, a die coater, or subsequently a blade coater, or the like can be used.
- the coating thickness can be adjusted by selecting the number of applications, a mesh of the screen, and a viscosity of the paste.
- an exposure step is performed.
- the exposure step generally exposure is performed through a photomask as in usual photolithography. Alternatively, a method of directly making a drawing by laser light, etc. without using a photomask may be used.
- a proximity exposure machine or the like can be used. When exposure of a large area is performed, a large area can be exposed with an exposure machine having a small exposure area by performing exposure while carrying out conveyance after applying the photosensitive paste onto the substrate.
- the active light ray used at this time include a near infrared ray, a visible light ray and an ultraviolet ray.
- the ultraviolet ray is most preferable, and as a light source thereof, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a germicidal lamp or the like can be used, but the ultra-high pressure mercury lamp is preferred.
- Exposure conditions vary depending on a thickness of the photosensitive paste coating film, and usually exposure is preferably performed for 0.01 to 30 minutes using an ultra-high pressure mercury lamp with a power of 1 to 100 mW/cm 2 .
- Lt, Lh and Lb can be appropriately changed by selecting optimum exposure conditions according to an exposure machine and materials to be used. If the exposure amount is decreased, Lt/Lh easily increases and Lb/Lh easily decreases. Conversely, if the exposure amount is increased, Lt/Lh easily decreases and Lb/Lh easily increases.
- development is performed using a difference in solubility in a developer between an exposed part and an unexposed part of the photosensitive paste coating film, thereby obtaining a desired grid-shaped photosensitive paste coating film pattern.
- Development is performed using a dipping method, a spray method or a brush method.
- a solvent capable of dissolving the organic component in the paste can be used.
- the developer is mainly composed of water.
- development can be performed with an alkali aqueous solution.
- an inorganic alkali aqueous solution such as that of sodium hydroxide, sodium carbonate or calcium hydroxide can be used, but use of an organic alkali aqueous solution is more preferable because an alkali component is easily removed during firing.
- the organic alkali include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine.
- the concentration of the alkali aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass.
- the development temperature during development is preferably 20 to 50°C in terms of process control.
- a firing step is performed in a firing furnace.
- the atmosphere and temperature for the firing step vary depending on the types of the photosensitive paste and the substrate, but firing is performed in air or in an atmosphere of nitrogen, hydrogen or the like.
- a batch-type firing furnace or a belt-type continuous firing furnace can be used.
- firing is performed by keeping normally at the temperature of 500 to 700°C for 10 to 60 minutes.
- the firing temperature is more preferably 500 to 650°C.
- the firing temperature being lower than 500°C is not preferable because sintering of the barrier rib pattern does not proceed, and the strength of the barrier rib obtained decreases.
- the firing temperature being higher than 650°C is not preferable because the bottom of the pattern is thickened due to softening of the barrier rib glass, so that Lb/Lh easily becomes greater than 3.
- the organic component is removed from the grid-shaped photosensitive paste coating film pattern, and the low-melting-point glass contained in the coating film pattern is softened and sintered to obtain a barrier rib member in which a grid-like barrier rib substantially composed of an inorganic substance is formed on a substrate.
- a reflecting film is formed on a surface of the barrier rib and a substrate surface which is not provided with the barrier rib.
- the material of the reflecting film is not particularly limited, but use of a material which is pervious to X-rays and reflects visible light, an electromagnetic wave of 300 to 800 nm emitted by the phosphor, is preferable.
- a metal such as Ag, Au, Al, Ni or Ti or a metal oxide, which is less degradable is preferable.
- the surface of the barrier rib refers to a surface of the barrier rib except for a surface where the barrier rib and the substrate are not in contact with each other, i.e. the top of the barrier rib and the side surface of the barrier rib.
- the reflecting film after formation of the barrier rib is preferable because reflecting films having the same material can be simultaneously formed on the surface of the barrier rib and the substrate surface which is not provided with the barrier rib. As a result, reflecting films having similar reflectivities can be formed on the side surface of the barrier rib and the substrate surface, so that visible light emitted by the phosphor can be uniformly guided to the sensor side more efficiently. It is preferable that a reflecting film is not formed on the substrate surface before formation of the barrier rib. In other words, it is preferable that a deflecting film is not formed on the surface where the barrier rib and the substrate are in contact with each other. This is because in the step of exposing the barrier rib, exposure light is scattered by the reflecting film, so that a high-definition pattern cannot be formed.
- the method for forming a reflecting film is not particularly limited, and various kinds of film formation methods can be used such as a method in which a reflecting material is made pasty, applied to the surface, and then fired to remove a solvent, and a method in which a reflecting material is injected by a spray.
- a vacuum film formation method such as vacuum deposition, sputtering, ion plating, CVD or laser ablation is preferable because a uniform reflecting film can be formed at a lower temperature, and sputtering is more preferable because a uniform film can be formed on the side surface of the barrier rib. If a temperature higher than the firing temperature of the barrier rib is applied during formation of the reflecting film, the barrier rib is deformed, and therefore the temperature during formation of the reflecting film is preferably lower than the temperature during formation of the barrier rib.
- a phosphor is filled in cells divided by the barrier rib, whereby a scintillator panel can be completed.
- the cell refers to a space divided by a grid-like barrier rib.
- the phosphor filled in the cell is referred to as a scintillator layer.
- the phosphor various known phosphor materials can be used. Particularly, a material having a high conversion rate of an X-ray to visible light, such as CsI, Gd 2 O 2 S Lu 2 O 2 S Y 2 O 2 S, LaCl 3 , LaBr 3 , LaI 3 , CeBr 3 , CeI 3 , LuSiO 5 or Ba (Br, F, Zn), is used, but the phosphor is not limited thereto. For enhancing luminous efficiency, various kinds of activators may be added.
- CsI a mixture of CsI and sodium iodide (NaI) in an arbitrary molar ratio, or CsI containing activation substances such as indium (In), thallium (Tl), lithium (Li), potassium (K), rubidium (Rb) or sodium (Na) is preferable.
- a thallium compound such as thallium bromide (TlBr), thallium chloride (TlCl) or thallium fluoride (TlF, TlF 3 ) can also be'used as an activator.
- a method in which crystalline CsI is deposited by vacuum deposition in this case, it is also possible to co-deposit a thallium compound such as thallium bromide
- the amount of the phosphor filled in cells divided by the barrier rib is preferably 50% to 100% in terms of a volume fraction of the phosphor.
- the volume fraction of the phosphor in cells is referred to as a phosphor filling ratio. If the phosphor filling ratio is less than 50%, efficiency with which incident X-rays are converted to visible light is low. For enhancing conversion efficiency of incident X-rays, efficiency of conversion into visible light can be enhanced by increasing the aspect ratio of the barrier rib height to the barrier rib pitch, but it is preferable to fill the' phosphor in the space of the cell with a high density because efficiency can be further enhanced.
- a light shielding film between the barrier rib and the reflecting film.
- the material of the light shielding film is not particularly limited, and a metal film of chromium, nichrome, tantalum or the like, a resin containing a black pigment such as carbon, or the like can be used.
- the method for forming a light shielding film is not particularly limited, and a method including applying a pasty material, or various kinds of vacuum film formation methods can be used.
- Raw materials used for the barrier rib photosensitive paste of Examples are as follows.
- Photosensitive monomer trimethylolpropane triacrylate
- Photosensitive polymer product of addition reaction of 0.4 equivalents of glycidyl methacrylate to carboxyl groups of a copolymer of methacrylic acid/methyl methacrylate/styrene in a mass ratio of 40/40/30 (weight average molecular weight: 43000, acid value: 100)
- Photo-polymerization initiator
- An organic solution having the composition shown in Table 1 was prepared.
- the compositions shown in Table 1 are all based on parts by mass.. 10 parts by mass of a photosensitive monomer, 24 parts by mass of a photosensitive polymer, 6 parts by mass of a photo-polymerization initiator, 0.2 part by mass of a polymerization inhibitor and 12.8 parts by mass of an ultraviolet ray absorber solution were dissolved in 38 parts by mass of an organic solvent under heating at a temperature of 80°C. After the obtained solution was cooled, 9 parts by mass of a viscosity modifier was added to prepare an organic solution 1.
- the refractive index (ng) of an organic coating film obtained by applying the organic solution 1 to a glass substrate and drying the applied solution was 1.553.
- the barrier rib photosensitive paste A was applied to a glass substrate of 500 mm x 500 mm ("OA-10" manufactured by NIPPON ELECTRIC GLASS Co., Ltd.) by a die coater so as to have a dry thickness of 580 ⁇ m, and dried to form a barrier rib photosensitive paste coating film.
- the barrier rib photosensitive paste coating film was exposed at 700 mJ/cm 2 by an ultra-high pressure mercury lamp through a photomask (chrome mask) having a grid-like opening corresponding to a barrier rib pattern and having pitch of 160 ⁇ m.
- the exposed barrier rib photosensitive paste coating film was developed in a 0.5% aqueous ethanolamine solution, so that an unexposed part was removed to form a grid-like photosensitive paste coating film pattern. Further, the photosensitive paste coating film pattern was fired in air at 585°C for 15 minutes to remove organic components and soften and sinter the low-melting-point glass, thereby obtaining a grid-like barrier rib.
- an oxysulfide gadolinium having a particle diameter of 5 ⁇ m was mixed with ethyl cellulose, and the mixture was then filled in cells divided by the grid-like barrier rib, and was fired at 450°C to form a scintillator layer having a phosphor filling ratio of 90%, thereby preparing a scintillator panel 1.
- the shape of the cross section of the formed barrier rib was observed with a scanning electron microscope. In the case of a shape as shown in Fig. 1, 2 , 3 or 5 , Lt, Lh and Lb were calculated. When it was difficult to measure Lt or Lb as in Fig. 2 or 6 , L90 in place of Lt or L10 in place of Lb was measured. Measurement results are shown in Table 4. The shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Example 1 was similar to that in Fig. 3 .
- the obtained scintillator panel 1 was evaluated for (1) peeling or breakage of the barrier rib and (2) coating uniformity of the phosphor. Evaluation results are shown in Table 4. A sample free from defects for all the evaluation items was rated good. In Example 1, good results were obtained with the barrier rib and phosphor being free from defects.
- a photoelectric conversion element including a PIN type photodiode and a TFT and having a pixel size of 160 ⁇ m x 160 ⁇ m was disposed on a glass substrate in a matrix form, and a wiring portion including a bias wiring for applying a bias to the PIN type photodiode, a driving wiring for applying a driving signal to the TFT, a signal wiring for outputting a signal charge transferred by the TFT, and so on was formed to prepare an output substrate.
- the output substrate and the scintillator panel 1 were bonded to each other with a adhesive, which contained a hot melt resin and had a thickness of 10 ⁇ m, interposed therebetween so that the photoelectric converter and the scintillator layer faced each other, thereby completing an X-ray detector.
- Example 1 For the prepared X-ray detector, X-rays at a tube voltage of 80 kVp were applied from the substrate side of the scintillator panel to photograph a solid image, and the photograph was observed to evaluate light emitting characteristics. Evaluation results are shown in Table 4. A sample free from image defects such as crosstalk or pixel defects, and luminance reduction or unevenness was rated good. In Example 1, images, which were free from image defects and had a high luminance and a high definition, were obtained.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, and the exposure amount in the exposure step was changed to 1000 mJ/cm 2 .
- the prepared scintillator panel and X-ray. detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as' shown in Table 1, and the exposure amount in the exposure step was changed to 1000 mJ/cm 2 .
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the dry thickness of the barrier rib photosensitive paste coating film was changed to 350 ⁇ m, the exposure amount in the exposure step was changed to 630 mJ/cm 2 , and the pitch of the photomask and the photoelectric conversion element was 80 ⁇ m.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 4 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the exposure amount in the exposure step was changed to 900 mJ/cm 2 , and the barrier rib firing temperature was changed to 595°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 4 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the exposure amount in the exposure step was changed to 520 mJ/cm 2 , and the barrier rib firing temperature was changed to 595°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 1000 ⁇ m, the exposure amount in the exposure step was changed to 1100 mJ/cm 2 , and the pitch of the photomask and the photoelectric conversion element was changed to 210 ⁇ m.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 7 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, and the exposure amount in the exposure step was changed to 900 mJ/cm 2 .
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 7 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 920 mJ/cm 2 .
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 1100 mJ/cm 2 .
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 1000 mJ/cm 2 .
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 630 ⁇ m, the exposure amount in the exposure step was changed to 850 mJ/cm 2 , and the barrier rib firing temperature was changed to 650°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 255 ⁇ m, the exposure amount in the exposure step was changed to 690 mJ/cm 2 , and the barrier rib firing temperature was changed to 650°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 360 ⁇ m, the exposure amount in the exposure step was changed to 550 mJ/cm 2 , the barrier rib firing temperature was changed to 635°C, and the pitch of the photomask and the photoelectric conversion element was changed to 80 ⁇ m.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the exposure amount in the exposure step was changed to 900 mJ/cm 2 , the barrier rib firing temperature was changed to 635°C, and the pitch of the photomask and the photoelectric conversion element was changed to 80 ⁇ m.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Photosensitive monomer 10 20 8 10 10 10 Photosensitive polymer 24 24 23 23 23 23 Photopolymerization initiator 1.5 1.5 1.5 6 6 6 6 Ultraviolet ray absorber solution 9.6 9.6 9.6 12.8 12.8 9.6 9.6 Organic solvent 38 38 39 39 39 39 Polymerization inhibitor 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Viscosity modifier 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9
- a barrier rib was prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, and the low-melting-point glass powder A was changed to the low-melting-point glass powder C.
- the prepared barrier rib was evaluated in the same manner as in the case of the scintillator panel 1. Evaluation results are shown in Table 6.
- the refractive index of the low-melting-point glass as a raw material of the barrier rib photosensitive paste is low, exposure light does not reach the bottom of the barrier rib. Accordingly, the shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Comparative Example 1 was similar to that in the schematic view of Fig. 5 , so that a large number of peelings, breakages and torsions occurred in the barrier rib.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the low-melting-point glass powder A was changed to the low-melting-point glass powder C, the exposure amount in the exposure step was changed to 1000 mJ/cm 2 , and the barrier rib firing temperature was changed to 650°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. Exposure light reached the bottom of the barrier rib, but the shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Comparative Example 2 was similar to that in the schematic view of Fig. 6 , so that a large number of breakages of the barrier rib and protrusions with the phosphor flowing out from cells occurred. For light emitting characteristics, luminance unevenness and considerable luminance reduction occurred.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 1000 ⁇ m, the exposure amount in the exposure step was changed to 2000 mJ/cm 2 , and the pitch of the photomask and the photoelectric conversion element was changed to 210 ⁇ m.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. The bottom of the barrier rib was significantly thick, and considerable luminance reduction occurred.
- a scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the low-melting-point glass powder A was changed to the low-melting-point glass powder D, and the firing temperature was changed to 530°C.
- the prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. The height of the barrier rib was low, the bottom of the barrier rib was significantly thick, and considerable luminance reduction occurred due to coating failure of the phosphor.
- a screen printing paste 50 parts by mass of a terpineol solution containing 10% by mass of ethyl cellulose and 50 parts by mass of the low-melting-point glass powder A were mixed to prepare a screen printing paste.
- the refractive index (ng) of an organic coating film obtained by applying a terpineol solution, which contained 10% by mass of ethyl cellulose, to a glass substrate and drying the applied solution was 1.49.
- the printing paste was repeatedly applied in a film thickness of 40 ⁇ m by screen printing and dried for 12 layers using a pattern having pitches of 160 ⁇ m in longitudinal and traverse directions, an opening length of 125 ⁇ m x 125 ⁇ m, a wall width of 35 ⁇ m and a size appropriate to a predetermined number of pixels.
- Example 1 Example 2* Example 3* Example 4
- Example 5 Example 6
- Example 7 Example 8 Similar cross section shape Fig. 3 Fig. 2 Fig. 2 Fig. 1 Fig. 4 Fig. 4 Fig. 3 Fig.
- Example 9 Example 10
- Example 11 Example 12* Example 13* Example 14
- the scintillator panel of the present invention is provided with a barrier rib, which has high luminous efficiency and is free from distortion and the like, in a large area and with high accuracy, and can provide sharp images having reduced image unevenness and linear noises.
- the present invention can be suitably used as a scintillator panel which constitutes a radiation detector that is used for a medical diagnostic apparatus, a nondestructive inspection instrument and the like.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Toxicology (AREA)
- Electromagnetism (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Measurement Of Radiation (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
Abstract
Description
- The present invention relates to a scintillator panel which constitutes a radiation detector that is used for a medical diagnostic apparatus, a nondestructive inspection instrument and the like.
- X-ray images using films have been widely used heretofore in medical settings. However, the X-ray image using a film provides analog image information, and in recent years, digital radiation detectors such as computed radiography (CR) and flat panel radiation detectors (flat panel detectors: FPDs) have been developed.
- In a flat panel X-ray detector (FPD), a scintillator panel is used for converting a radiation into visible light. The scintillator panel contains,an X-ray phosphor such as cesium iodide (CsI), the X-ray phosphor emits visible light in response to an applied X-ray, and the emitted light is converted into an electric signal by a TFT (thin film transistor) or a CCD (charge-coupled device) to thereby convert X-ray information into digital image information. However, the FPD has a problem of low S/N ratio. This is attributable to scattering of visible light by the X-ray phosphor itself when the X-ray phosphor emits light, etc. For reducing influences of the scattering of light, methods of filling an X-ray phosphor in cells divided by a barrier rib have been proposed (
Patent Documents 1 to 4). - The shape of the barrier rib varies depending on a pitch, but the width is approximately 5 to 40 µm, and the height is approximately 100 to 800 µm.
- The method which has been heretofore used as a method for forming the barrier rib is a method of etching a silicon wafer, or a method in which a glass paste, a mixture of a pigment or a ceramic powder and a low-melting-point glass powder, is pattern-printed in multiple layers using a screen printing method, and then fired to form a barrier rib. However, in the method of etching a silicon wafer, the size of a scintillator panel that can be formed is restricted by the size of a silicon wafer, and a scintillator panel having a large size of, for example, 500 mm square cannot be obtained. A plurality of small-size panels should be arranged for making a large-size panel, but production of a scintillator panel in this way is difficult in terms of accuracy, and it is difficult to prepare a large-area scintillator panel.
- In the multi-layer screen printing method using a glass paste, processing of high accuracy is difficult due to a dimensional variation of a screen printing plate, etc. Further, when multi-layer screen printing is performed, a definite barrier rib width is required for enhancing the strength of a barrier rib in order to prevent destructive defects of the barrier rib. However, if the width of the barrier rib increases, a space between barrier ribs becomes relatively small, so that a volume available for filling an X-ray phosphor decreases, and the filling amount is not uniform. Therefore, a scintillator panel obtained in this method has the disadvantage that the amount of an X-ray phosphor is so small that the luminescence is reduced, and luminous unevenness occurs. This disadvantage makes it difficult to photograph sharp images in photographing in a low radiation dose.
- That is, for preparing a scintillator panel which has high luminous efficiency and provides sharp images, a technique for processing a barrier rib, which is capable of processing the barrier rib with high accuracy over a large area and narrowing the width of the barrier rib, and a technique for preventing visible light, which is emitted by an X-ray phosphor, from being leaked to outside are required.
-
- Patent Document 1: Japanese Patent Laid-open Publication No.
5-60871 - Patent Document 2: Japanese Patent Laid-open Publication No.
5-188148 - Patent Document 3: Japanese Patent Laid-open Publication No.
2011-007552 - Patent Document 4: Japanese Patent Laid-open Publication No.
2011-021924 - An object of the present invention is to solve the above-described disadvantages and provide a scintillator panel which is provided with a narrow barrier rib with high accuracy in a large area, has high luminous efficiency, and provides sharp images.
- The above-described object is achieved by any of the following technical means.
- (1) A scintillator panel including: a plate-like substrate; a barrier rib provided on the substrate; and a scintillator layer including a phosphor filled in cells divided by the barrier rib, wherein the barrier rib is formed of a material which is mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide, a value obtained by dividing a top width Lt of the barrier rib or a 90%-height width L90 of the barrier rib by a half-value width Lh of the barrier rib is 0.45 to 1, and a value obtained by dividing a bottom width Lb of the barrier rib or a 10%-height width L10 of the barrier rib by the half-value width Lh is 1 to 3.
- (2) The scintillator panel according to (1), wherein a pitch P of the barrier rib is 50 to 120 µm, the half-value width Lh is 5 to 30 µm, and a height H of the barrier rib is 100 to 500 µm.
- (3) The scintillator panel according to (1), wherein the pitch P of the barrier rib is 120 to 240 µm, the half-value width Lh is 10 to 40 µm, and the height H of the barrier rib is 200 to 800 µm.
- (4) The scintillator panel according to any one of (1) to (3), wherein a line that connects the end of the central portion of the barrier rib to the bottom surface of the barrier rib at a cross section perpendicular to the longitudinal direction in the barrier rib is a curved line.
- (5) The scintillator panel according to any one of (1) to (4), wherein a reflecting film is formed on a surface of the barrier rib.
- (6) A method for manufacturing the scintillator panel according to any one of (1) to (5), the method including: a step of forming a photosensitive paste coating film by applying onto a substrate a photosensitive paste which contains a low-melting-point glass and a photosensitive organic component; an exposure step of exposing the obtained photosensitive paste coating film to light in a predetermined pattern; a development step of dissolving and removing a part of the exposed photosensitive paste coating film which is soluble in a developer; a firing step of heating the photosensitive paste coating film pattern after development to a firing temperature of 500°C to 700°C to remove the organic component and soften and sinter the low-melting-point glass and thereby forming a barrier rib; and a step of filling a phosphor.
- According to the present invention, a barrier rib having a high strength can be formed with high accuracy in a large area, and visible slight emitted by a phosphor can be efficiently utilized, so that there can be provided a scintillator panel which has a large size and provides sharp images, and a method for manufacturing the scintillator panel.
-
-
Fig. 1 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib of a first aspect in the present invention. -
Fig. 2 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib of a second aspect in the present invention. -
Fig. 3 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib of a third aspect in the present invention. -
Fig. 4 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib of a fourth aspect in the present invention. -
Fig. 5 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib that is not encompassed by the present invention. -
Fig. 6 is a schematic view showing a cross section perpendicular to the longitudinal direction in a barrier rib that is not encompassed by the present invention. -
Fig. 7 is a sectional view schematically showing the configuration of a radiation detector including a scintillator panel of the present invention. -
Fig. 8 is a perspective view schematically showing the configuration of the scintillator panel of the present invention. - The preferred configurations of a scintillator panel of the present invention and a radiation detector using the scintillator panel will be described below with reference to the drawings, but the present invention is not limited thereto.
-
Fig. 7 is a sectional view schematically showing the configuration of a radiation detector including a scintillator panel of the present invention.Fig. 8 is a perspective view schematically showing the configuration of the scintillator panel of the present invention. Aradiation detector 1 includes ascintillator panel 2, an output substrate 3 and apower supply portion 12. Thescintillator panel 2 includes ascintillator layer 7 including a phosphor, and absorbs energy of an incident radiation such as an X-ray to emit an electromagnetic wave having a wavelength ranging from 300 to 800 nm, i.e. an electromagnetic wave (light) which ranges from ultraviolet light to infrared light with visible light at the center. - The
scintillator panel 2 includes asubstrate 4, a grid-like barrier rib 6 formed on the substrate and intended for dividing cells, and ascintillator layer 7 including a phosphor filled in a cell formed by the barrier rib. By further forming abuffer layer 5 between thesubstrate 4 and the barrier rib 6, the barrier rib 6 can be stably formed. It is preferable that a reflectingfilm 13 is formed on the barrier rib 6 and thesubstrate 4. Owing to the reflectingfilm 13, visible light emitted by the phosphor can be reflected without passing through the barrier rib 6, and resultantly light emitted at thescintillator layer 7 can be made to reach a photoelectric conversion layer 9 on the output substrate 3 efficiently. - The output substrate 3 has the photoelectric conversion layer 9 in which pixels including photosensors and TFT are two-dimensionally formed, and an
output layer 10 on a substrate 11. When the light exit surface of thescintillator panel 2 and the photoelectric conversion layer 9 of the output substrate 3 are bonded or adhered to each other with adiaphragm layer 8, which contains a polyimide resin or the like, interposed therebetween, theradiation detector 1 is formed. Light emitted at thescintillator layer 7 reaches the photoelectric conversion layer 9, undergoes photoelectric conversion at the photoelectric conversion layer 9, and generates output. In the scintillator panel of the present invention, each cell is divided by a barrier rib, and therefore when the size and pitch of pixels of a photoelectric conversion element arranged in a grid-like shape are made coincident with the size and pitch of cells of the scintillator panel, scattered light can be prevented from reaching a neighboring cell even though light is scattered by a phosphor. In this way, blurring of images resulting from light scattering can be reduced, so that high-accuracy photographing is possible. - The barrier rib that forms the scintillator panel of the present invention is required to satisfy the following requirement: a value obtained by dividing Lt by Lh is 0.45 to 1 and a value obtained by dividing Lb by Lh is 1 to 3 where Lt is a top width of the barrier rib, Lh is a half-value width of the barrier rib, and Lb is a bottom width of the barrier rib. For securing the strength of the phosphor filling space and the barrier rib, the value obtained by dividing Lt by Lh is preferably 0.6 to 1, more preferably 0.8 to 1, further preferably 0.8 to 0.95. The value obtained by dividing Lb by Lh is preferably 1 to 2, more preferably 1 to 1.5, further preferably 1.3 to 1.5. Lt, Lh and Lb in the barrier rib of the first aspect are shown in
Fig. 1 . Here, Lh refers to a line width of a portion at a height of 50 from the bottom surface of the barrier rib where the height of the barrier rib is 100 (hereinafter, referred to as "barrier rib central portion") at a cross section perpendicular to the longitudinal direction in the barrier rib. - If Lt/Lh is more than 1, constriction occurs at the periphery of the central portion of the barrier rib, so that filling amount of the phosphor to the pitch of the barrier rib decreases, and an opening for extracting light emitted by the phosphor is narrowed, leading to a decrease in luminance. Besides, nonuniformity such as coating unevenness and thickness unevenness occurs at the time of filling the phosphor. On the other hand, if Lt/Lh is less than 0.45, the top of the barrier rib becomes extremely narrow, causing a shortage of strength for sustaining a pressure applied at the time of bonding the scintillator panel to a light detection substrate, so that the top of the barrier rib may be easily collapsed, or the barrier rib may be cut at some midpoint, leading to occurrence of breakage.
- If Lb/Lh is less than 1, the strength of the barrier rib decreases, so that falling, breakage or torsion of the barrier rib occurs. On the other hand, if Lb/Lh is more than 3, the filling amount of the phosphor decreases, so that the luminance decreases.
- The shape of the barrier rib described above can be controlled by changing various conditions described later.
- When the top of the barrier rib is rounded, or the bottom of the barrier rib is trailed, so that it is difficult to exactly perceive the top of the barrier rib or the bottom of the barrier rib, a 90%-height width (L90) in place of Lt or a 10%-height width (L10) in place of Lb can be used. In this case, it is necessary that a value obtained by dividing L90 by Lh be 0.45 to 1, and a value obtained by dividing L10 by Lh be 1 to 3. The value obtained by dividing L90 by Lh is preferably 0.8 to 1, and the value obtained by dividing L10 by Lh is preferably 1 to 1.5. L90, Lh and L10 in the barrier rib of the second aspect are shown in
Fig. 2 . Here, L90 refers to a line width of a portion at a height of 90 from the bottom surface of the barrier rib where the height of the barrier rib is 100 at a cross section perpendicular to the longitudinal direction in the barrier rib. Here, L10 refers to a line width of a portion at a height of 10 from the bottom surface of the barrier rib where the height of the barrier rib is 100 at a cross section perpendicular to the longitudinal direction in the barrier rib. - Various kinds of line widths of the barrier rib, such as Lt, Lb, L90, L10 and Lh, can be each calculated by repeatedly measuring 25 random spots on the formed barrier rib with a scanning electron microscope (for example, "S-4800" manufactured by Hitachi, Ltd.), and determining an average thereof.
- More specifically, the measurement with a scanning electron microscope can be made in the following manner. First, the barrier rib is cut at right angles to the stripe direction of the barrier rib, i.e. the longitudinal direction, so that the cross section of the barrier rib is as shown in
Fig. 1 etc., and the cross section is processed to a size available for observation with a scanning electron microscope. As a measurement magnification, a magnification is selected so that the visual field includes 2 to 5 barrier ribs. For example, when the pitch of the barrier rib is 160 µm, a magnification of 200 to 300 may be selected. Thereafter, the reduced scale can be calibrated with a standard sample having a size comparable to the line width of the barrier rib, followed by taking a picture, and calculating a line width from the reduced scale. - The line S that connects the end of the central portion of the barrier rib to the end of the bottom surface of the barrier rib at a cross section perpendicular to the longitudinal direction in the barrier rib is not limited to a straight line as shown in
Fig. 1 , and may be a curved line having a curvature radius R as shown inFig. 4 . The line S is preferably a curved line because even when the value obtained by dividing Lb by Lh increases, a wide phosphor filling space can be secured, so that the luminance does not decrease. The curvature radius R of the line S is preferably Lh or greater. - Lh is preferably 5 to 40 µm. If Lh is more than 40 µm, the opening ratio decreases, so that a sufficient luminance is not obtained. On the other hand, if Lh is less than 5 µm, the barrier rib has an insufficient strength, resulting in occurrence of falling or torsion of the barrier rib.
- For providing definite and sharp images, the pitch of the barrier rib is preferably 30 to 300 µm, more preferably 50 to 240 µm.
- The height of the barrier rib is preferably 50 to 3000 µm, more preferably 100 to 800 µm. If the height of the barrier rib is less than'50 µm, sufficient luminance is not obtained. On the other hand, if the height of the barrier rib is more than 3000 µm, luminous efficiency decreases.
- For observing a more definite X-ray image with a low exposure amount, it is preferable that where P is the pitch of the barrier rib and H is the height of the barrier rib, the barrier rib has a shape in which Lh is 5 to 30 µm and H is 100 to 500 µm when P is 50 to 120 µm. Preferably, Lh is 10 to 40 µm and H is 200 to 800 µm when P is 120 to 240 µm.
- The material of the substrate to be used for the scintillator panel of the present invention is preferably a material pervious to radiations, and various kinds of glasses, polymer materials, metals and the like can be used. For example, a glass plate containing a glass such as quartz, borosilicate glass or chemically reinforced glass; a ceramic substrate containing a ceramic such as sapphire, silicon nitride, silicon carbide; a semiconductor substrate containing a semiconductor such as silicon, germanium, gallium arsenide, gallium phosphide or gallium nitrogen; a polymer film (plastic film) such as a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, a triacetate film, a polycarbonate film or a carbon fiber reinforced resin sheet; a metal sheet such as an aluminum sheet, an iron sheet or a copper sheet; a metal sheet having a coating layer of a metal oxide, or an amorphous carbon substrate; or the like can be used. Particularly, a glass plate is preferable in terms of flatness and heat resistance. Further, since weight reduction of the scintillator panel is promoted for pursuing convenience of transportation of the scintillator panel, the glass plate is preferably a thin glass.
- A barrier rib is formed on the substrate. The barrier rib is required to be formed of a material which is mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide in terms of durability, heat resistance and high-definition processing. The material which is mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide has a proper refractive index and a softening temperature, and is suitable for forming a narrow barrier rib in a large area and with high accuracy. The low-melting-point glass refers to a glass having a softening temperature of 700°C or lower. The phrase "mainly composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide" means that a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide constitutes 50 to 100% by mass of a material that forms the barrier rib.
- A method for manufacturing the scintillator panel of the present invention includes: a step of forming a photosensitive paste coating film by applying onto a substrate a photosensitive paste which contains a low-melting-point glass and a photosensitive organic component; an exposure step of exposing the obtained photosensitive paste coating film to light in a predetermined pattern; a development step of dissolving and removing a part of the exposed photosensitive paste coating film which is soluble in a developer; a firing step of heating the photosensitive paste coating film pattern after development to a firing temperature of 500 to 700°C to remove the organic component and soften and sinter the low-melting-point glass and thereby forming a barrier rib; forming a metallic reflecting film at a temperature lower than the firing temperature using a vacuum film formation method; and a step of filling a phosphor.
- In the exposure step, a necessary part of the photosensitive paste coating film is photocured, or an unnecessary part of the photosensitive paste coating film is photodecomposed by exposure to add a contrast of dissolution of the photosensitive paste coating film in a developer. In the development step, an unnecessary part of the exposed photosensitive paste coating film is removed with a developer, so that a photosensitive paste coating film pattern in which only a necessary part of the coating film remains is obtained.
- In the firing step, the obtained photosensitive paste coating film pattern is fired at a temperature of 500 to 700°C, preferably 500 to 650°C, whereby the organic component is decomposed and distilled away, and the low-melting-point glass is softened and sintered to form a barrier rib containing a low-melting-point glass. For completely removing the organic component, the firing temperature is preferably 500°C or higher. If the firing temperature is higher than 700°C, deformation of the substrate increases when a general glass substrate is used as the substrate, and therefore the firing temperature is preferably 700°C or lower.
- The method of the present invention is capable of processing with high accuracy as compared to a processing method in which a glass paste is printed by laminating by a multi-layer screen printing and then fired.
- The photosensitive paste for use in the present invention is formed of an organic component containing a photosensitive organic component, and an inorganic powder containing a low-melting-point glass containing 2 to 20% by-mass of an alkali metal oxide. The organic component is required in a definite amount for forming a photosensitive paste coating film pattern before firing, but if the amount of the organic component is excessively large, the amount of substances removed in the firing step increases, so that the shrinkage rate after firing becomes large, and therefore pattern defects easily occur in the firing step. On the other hand, an excessively small amount of the organic component may not be preferable because miscibility and dispersibility of an inorganic powder in the paste are deteriorated, so that not only defects easily occur during firing, but also coatability of the paste is deteriorated due to an increase in viscosity of the paste, and further the stability of the paste is adversely affected. Thus, the content of the inorganic powder in the photosensitive paste is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. The content of the inorganic powder being less than 30% by mass is not preferable because the shrinkage rate during firing increases to cause breakage and peeling of the barrier rib. Further, pattern thickening and remaining of a film during development easily occur, and Lb/Lh easily becomes greater than 3. Therefore the content of less than 30% by mass is not preferable. On the other hand, if the content of the inorganic powder is more than 80% by mass, the amount of the photosensitive organic component decreases, so that the photosensitive paste coating film is not photocured to the bottom in the exposure step. As a result, Lt/Lh easily becomes greater than 1, and Lb/Lh easily becomes smaller than 1. Therefore, the content of more than 80% by mass is not preferable.
- The content of the low-melting-point glass is preferably 50 to 100% by mass based on the total of the inorganic powder. The content of the low-melting-point glass being less than 50% by mass with respect to the inorganic powder is not preferable because sintering does not properly proceed in the firing step, and therefore the strength of the barrier rib obtained decreases.
- For ensuring that in the firing step, the organic component is almost completely removed and the barrier rib obtained has a definite strength, it is preferable to use a low-melting-point glass containing a low-melting-point glass having a softening temperature of 480°C or higher. If the softening temperature is lower than 480°C, the low-melting-point glass is softened before the organic component is sufficiently removed during firing, so that residues of the organic component are captured in the glass. In this case, the organic component may be gradually released later to deteriorate product quality. Further, residues of the organic component captured in the glass become a cause of coloring of the glass. When a low-melting-point glass powder having a softening temperature of 480°C or higher is used and firing is performed at 500°C or higher, the organic component can be completely removed. As described above, it is necessary that'the firing temperature be 500 to 700°C. Since the firing temperature is preferably 500 to 650°C, the softening temperature of the low-melting-point glass is preferably 480 to 680°C, more preferably 480 to 620°C.
- The softening temperature is determined by extrapolating a heat absorption completion temperature at an endothermic peak by a tangent method from a DTA curve obtained by measuring a sample using a differential thermal analyzer (DTA, "Differential Type Differential Thermal Balance TG8120" manufactured by Rigaku Corporation). Specifically, an inorganic powder as a measurement sample is measured by elevating the temperature at 20°C/minute from room temperature with an alumina powder as a standard sample using a differential thermal analyzer, thereby obtaining a DTA curve. A softening point Ts determined by extrapolating a heat absorption completion temperature at an endothermic peak by a tangent method from the obtained DTA curve is defined as a softening temperature.
- For obtaining a low-melting-point glass, a metal oxide selected from the group consisting of lead oxide, bismuth oxide, zinc oxide and alkali metal oxides, which are materials effective for lowering the melting point of glass, can be used. Particularly, it is preferable to adjust the softening temperature of glass using an alkali metal oxide. Generally the alkali metal refers to lithium, sodium, potassium, rubidium and cesium, but the alkali metal oxide for use in the present invention refers to a metal oxide selected from the group consisting of lithium oxide, sodium oxide and potassium oxide.
- In the present invention, it is necessary that the content X of an alkali metal oxide (M2O) in the low-melting-point glass be in a range of 2 to 20% by mass. If the content of the alkali metal oxide is less than 2% by mass, the softening temperature becomes high, and therefore it is necessary to perform the firing step at a high temperature. Accordingly, when a glass substrate'is used as the substrate, it is likely that the scintillator panel obtained is distorted or defects occur in the barrier rib due to deformation of the substrate in the firing step, and therefore the content of less than 2% by mass is not
suitable. If the content of the alkali metal oxide is more than 20% by mass, the viscosity of glass decreases too much in the firing step. Accordingly, the shape of the barrier rib obtained is easily distorted. Further, the porosity of the barrier rib obtained becomes excessively small, leading to a decrease in light emission luminance of the scintillator panel obtained. - Further, it is preferable to add 3 to 10% by mass of zinc oxide in addition to the alkali metal oxide for adjusting the viscosity of glass at a high temperature. If the content of zinc oxide is less than 3% by mass, the viscosity of glass at a high temperature becomes high, and addition of zinc oxide in an amount of more than 10% by mass tends to increase the cost of glass.
- Further, by including, in addition to the alkali metal oxide and zinc oxide, silicon oxide, boron oxide, aluminum oxide, an oxide of an alkali earth metal or the like in the low-melting-point glass, the stability, crystallinity, transparency, refractive index, thermal expansion characteristic or the like of the low-melting-point glass can be controlled. As a composition of the low-melting-point glass, the composition range shown below is preferable because a low-melting-point glass having a viscosity characteristic suitable for the present invention can be prepared.
- Alkali metal oxide: 2 to 20% by mass
- Zinc oxide: 3 to 10% by mass
- Silicon oxide: 20 to 40% by mass
- Boron oxide: 25 to 40% by mass
- Aluminum oxide: 10 to 30% by mass
- Alkali earth metal oxide: 5 to 15% by mass
- The alkali earth metal refers to one or more metal selected from the group consisting of magnesium, calcium, barium and strontium.
- The particle diameter of inorganic particles containing a low-melting-point glass can be evaluated using a particle size distribution analyzer ("MT 3300" manufactured by NIKKISO CO., LTD.). As a measurement method, an inorganic powder is charged in a sample chamber filled with water, and subjected to an ultrasonic treatment for 300 seconds, followed by performing a measurement.
- The 50% volume average particle diameter (D50) of the low-melting-point glass is preferably 1.0 to 4.0 µm. If D50 is less than 1.0 µm, agglomeration of particles becomes strong, so that it becomes difficult to achieve-uniform dispersibility, leading to unstable fluidity of a paste. In this case, thickness uniformity when a paste is applied is deteriorated. If D50 is more than 4.0 µm, the surface unevenness of a sintered body obtained increases, so that a pattern tends to be broken in a subsequent step.
- The photosensitive paste for use in the present invention may contain as a filler a high-melting-point glass that is not softened at 700°C, or ceramic particles such as those of silicon oxide, aluminum oxide, titanium oxide or zirconium oxide in addition to the above-described low-melting-point glass. The filler, when used together with the low-melting-point glass, has an effect of controlling the shrinkage rate after firing of a paste composition and retaining the shape of the barrier rib formed. However, if the ratio of the filler to the total of the inorganic powder is more than 50% by mass, sintering of the low-melting-point glass is hindered to cause a problem such as a reduction in strength of the barrier rib, and therefore the ratio of more than 50% by mass is not preferable. Preferably the filler has an average particle diameter of 0.5 to 4.0 µm for the same reason as that described for the low-melting-point glass.
- In the photosensitive paste for use in the present invention, the average refractive index n1 of the low-melting-point glass and the average refractive index n2 of the photosensitive organic component satisfy preferably -0.1 < n1 - n2 < 0.1, more preferably -0.01 ≤ n1 - n2 ≤ 0.01, further preferably -0.005 ≤ n1 - n2 ≤ 0.005. By satisfying the above-described requirement, light scattering at the interface between the low-melting-point glass and the photosensitive organic component is suppressed in the exposure step, so that pattern formation can be performed with high accuracy. On the other hand, if n1 - n2 < -0.01 or n1 - n2 > 0.01, light scattering easily occurs at the interface between the low-melting-point glass and the photosensitive organic component in the exposure step. As a result, if the exposure amount is small in the exposure step, light does not reach the bottom of the photosensitive paste coating film, and therefore Lt/Lh easily becomes greater than 1 and Lb/Lh easily becomes smaller than 1. Therefore, the relationship of n1 - n2 < -0.01 or n1 - n2 > 0.01 is not preferable. However, increasing the exposure amount is not preferable because the photosensitive paste coating film is cured by scattered light due to increased light scattering, so that Lt/Lh easily becomes smaller than 0.45 and Lb/Lh easily becomes greater than 3.
- By adjusting the compounding ratio of oxides that constitute the low-melting-point glass, a low-melting-point glass having both a preferable heat characteristic and a preferable average refractive index can be obtained.
- The refractive index of the low-melting-point glass can be measured using a Becke line detection method. A refractive index at 25°C and at a wavelength of 436 nm (g-line) was defined as the refractive index of the low-melting-point glass in the present invention. The average refractive index of the photosensitive organic component can be determined by measuring a coating film composed of a photosensitive organic component by ellipsometry. A refractive index at 25°C and at a wavelength of 436 nm (g-line) was defined as the average refractive index of the photosensitive organic component.
- When the photosensitive paste for use in the present invention includes a photosensitive organic component as an organic component, it can be pattern-processed by the photosensitive paste method described above. By using a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer, a photo-polymerization initiator or the like as the photosensitive organic component, reactivity can be controlled. Here, the photosensitivity in the photosensitive monomer, the photosensitive oligomer and the photosensitive polymer means that when the paste is irradiated with active light rays, the photosensitive monomer, the photosensitive oligomer or the photosensitive polymer undergoes a reaction of photo-crosslinking, photo-polymerization or the like to change the chemical structure.
- The photosensitive monomer is a compound having an active carbon-carbon double bond, and examples thereof include monofunctional compounds and polyfunctional compounds having a vinyl group, an acryloyl group, a methacryloyl group or an acrylamide group as a functional group. Particularly, it is preferable that the photosensitive organic component contains 10 to 80% by mass of a compound selected from the group consisting of polyfunctional acrylate compounds and polyfunctional methacrylate compounds from the viewpoint of increasing the crosslinking density during curing by a photoreaction to improve pattern formability. As the polyfunctional acrylate compounds and polyfunctional methacrylate compounds, a variety of kinds of compounds have been developed, and an appropriate one can be selected from those compounds in consideration of reactivity, a refractive index and the like.
- As the photosensitive oligomer or the photosensitive polymer, an oligomer or polymer having an active carbon-carbon unsaturated double bond is preferably used. The photosensitive oligomer or the photosensitive polymer is obtained by, for example, copolymerizing a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or an acid anhydride thereof, and a monomer such as a methacrylic acid ester, an acrylic acid ester, styrene, acrylonitrile, vinyl acetate or 2-hydroxy acrylate. As a method for introducing an active carbon-carbon unsaturated double bond into an oligomer or a polymer, a method can be used in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or acryl chloride, or a carboxylic acid such as maleic acid is reacted with a mercapto group, an amino group, a hydroxyl group or a carboxyl group in an oligomer or a polymer, etc.
- By using as the photosensitive monomer or the photosensitive oligomer a monomer or oligomer having a urethane bond, a photosensitive paste insusceptible to pattern defects in the firing step can be obtained. In the present invention, pattern defects are suppressed because rapid shrinkage is hard to occur in the process of sintering of a glass in the later stage of the firing step due to use of a low-melting-point glass as the glass. In addition, when a compound having a urethane structure is used for the organic component, stress is relaxed in the process of decomposition and distillation of the organic component in the early stage of the firing step, so that pattern defects are hard to occur. Owing to both the effects described above, pattern defects can be suppressed over a wide temperature range.
- The photo-polymerization initiator is a compound which generates radicals when irradiated with an active light ray. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyl diphenyl ketone, dibenzyl ketone, fluorenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyl methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene anthrone, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexanone, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 1-phetyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, Michler ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morphorino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, benzoin peroxide and eosine, and combinations of a photo-reductive pigments such as methylene blue and reducing agents such as ascorbic acid and triethanolamine. These compounds may be used in combination of two or more thereof.
- The content of the photo-polymerization initiator is not limited, but is preferably in a range of 0.05 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the photosensitive component. If the amount of the photo-polymerization initiator decreases, the photosensitivity decreases, and the barrier rib is thinned. If the amount of the photo-polymerization initiator increases, the barrier rib is thickened.
- It is also preferable that the photosensitive paste contains an ultraviolet ray absorber. By adding an ultraviolet ray absorber, a barrier rib having a high aspect ratio, a high definition and a high resolution can be obtained. The ultraviolet ray absorber is a compound having a high ultraviolet ray absorption effect. The ultraviolet ray absorber is preferably an organic dye, and particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo-based dyes, aminoketone-based dyes, xanthene-based dyes, quinoline-based dyes, aminoketone-based dyes, anthraquinone-based dyes, benzophenone-based dyes, diphenylcyanoacrylate-based dyes, triazine-based dyes, p-aminobenzoic acid-based dyes and the like can be used. The organic-based dye does not remain in the barrier rib after firing, and is therefore preferable. Among them, azo-based and benzophenone-based dyes are preferable. The amount of the ultraviolet ray absorber is not limited, but is preferably in a range of 0.1 to 60% by mass, more preferably 0.1 to 30% by mass with respect to the photosensitive component. The relationship between the amount of the ultraviolet ray absorber and the shape of the barrier rib obtained also depends on an absorption wavelength of the ultraviolet ray absorber. For example, in the case of an ultraviolet ray absorber having a high UV absorption coefficient in a range of 350 to 450 nm, Lt/Lh easily decreases and Lb/Lh easily increases if the amount of the ultraviolet ray absorber is large. Conversely, if the amount of the ultraviolet ray absorber is small, Lt/Lh easily increases and Lb/Lh easily decreases.
- The photosensitive paste may contain as a binder a copolymer having a carboxyl group. The copolymer having a carboxyl group is obtained by, for example, selecting a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or an acid anhydride thereof and other monomers such as a methacrylic acid ester, an acrylic acid ester, styrene, acrylonitrile, vinyl acetate or 2-hydroxy acrylate, and copolymerizing the monomers using an initiator such as azobisisobutyronitrile. As the copolymer having a carboxyl group, a copolymer having an acrylic acid ester or a methacrylic acid ester and an acrylic acid or a methacrylic acid as copolymerization components is preferably used because the thermal decomposition temperature during firing is low.
- The photosensitive paste is a paste excellent in solubility in an alkali aqueous solution when it contains a copolymer having a carboxyl group. The acid value of the copolymer having a carboxyl group is preferably 50 to 150 mg KOH/g. When the acid value is 150 mg KOH/g or less, the allowable range of development can be widened. When the acid value is 50 mg KOH/g or more, solubility of an unexposed part in a developer is not reduced. Therefore, it is not necessary to increase the concentration of a developer, and peeling of an exposed part is prevented, so that a high-definition pattern can be obtained. Further, it is also preferable that the copolymer having a carboxyl group has an ethylenically unsaturated group on a side chain. Examples of the ethylenically unsaturated group include an acryl group, a methacryl group, a vinyl group and an allyl group.
- The photosensitive paste is prepared by adding an organic solvent and a binder as required to a low-melting-point glass and a photosensitive organic component containing a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer, a photo-polymerization initiator or the like, and compounding various components so as to achieve a predetermined composition, followed by uniformly mixing and dispersing the mixture using a three-roll roller or a kneader.
- The viscosity of the photosensitive paste can be appropriately adjusted by the added ratios of an inorganic powder, a thickener, an organic solvent, a polymerization inhibitor, a plasticizer, a precipitation preventive agent and so on, and is preferably in a range of 2 to 200 Pa•s. For example, when the photosensitive paste is applied to the substrate by a spin coating method, a viscosity of 2 to 5 Pa•s is preferable. When the photosensitive paste is applied to the substrate by a screen printing method to achieve a film thickness of 10 to 20 µm in one application, a viscosity of 50 to 200 Pa•s is preferable. When a blade coater method, a die coater method or the like is used, a viscosity of 10 to 50 Pa•s is preferable.
- By applying the photosensitive paste thus obtained onto the substrate, forming a desired pattern by a photolithography method and performing firing, a barrier rib can be formed. An example of manufacturing a barrier rib by the photolithography method using the above-described photosensitive paste will be described, but the present invention is not limited thereto.
- The photosensitive paste is applied onto the whole or part of the substrate surface to form a photosensitive paste coating film. As an application method, a screen printing method, or a method using a bar coater, a roll coater, a die coater, or subsequently a blade coater, or the like can be used. The coating thickness can be adjusted by selecting the number of applications, a mesh of the screen, and a viscosity of the paste.
- Subsequently, an exposure step is performed. As the exposure step, generally exposure is performed through a photomask as in usual photolithography. Alternatively, a method of directly making a drawing by laser light, etc. without using a photomask may be used. As an exposure device, a proximity exposure machine or the like can be used. When exposure of a large area is performed, a large area can be exposed with an exposure machine having a small exposure area by performing exposure while carrying out conveyance after applying the photosensitive paste onto the substrate. Examples of the active light ray used at this time include a near infrared ray, a visible light ray and an ultraviolet ray. Among them, the ultraviolet ray is most preferable, and as a light source thereof, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a germicidal lamp or the like can be used, but the ultra-high pressure mercury lamp is preferred. Exposure conditions vary depending on a thickness of the photosensitive paste coating film, and usually exposure is preferably performed for 0.01 to 30 minutes using an ultra-high pressure mercury lamp with a power of 1 to 100 mW/cm2. Lt, Lh and Lb can be appropriately changed by selecting optimum exposure conditions according to an exposure machine and materials to be used. If the exposure amount is decreased, Lt/Lh easily increases and Lb/Lh easily decreases. Conversely, if the exposure amount is increased, Lt/Lh easily decreases and Lb/Lh easily increases.
- After exposure, development is performed using a difference in solubility in a developer between an exposed part and an unexposed part of the photosensitive paste coating film, thereby obtaining a desired grid-shaped photosensitive paste coating film pattern. Development is performed using a dipping method, a spray method or a brush method. For the developer, a solvent capable of dissolving the organic component in the paste can be used. Preferably the developer is mainly composed of water. When a compound having an acidic group such as a carboxyl group exists in the paste, development can be performed with an alkali aqueous solution. As the alkali aqueous solution, an inorganic alkali aqueous solution such as that of sodium hydroxide, sodium carbonate or calcium hydroxide can be used, but use of an organic alkali aqueous solution is more preferable because an alkali component is easily removed during firing. Examples of the organic alkali include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine. The concentration of the alkali aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass. If the alkali concentration is excessively low, a soluble part may not be removed, and if the alkali concentration is excessively high, a pattern part may be peeled and a non-soluble part may be corroded. The development temperature during development is preferably 20 to 50°C in terms of process control.
- Next, a firing step is performed in a firing furnace. The atmosphere and temperature for the firing step vary depending on the types of the photosensitive paste and the substrate, but firing is performed in air or in an atmosphere of nitrogen, hydrogen or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. Preferably firing is performed by keeping normally at the temperature of 500 to 700°C for 10 to 60 minutes. The firing temperature is more preferably 500 to 650°C. The firing temperature being lower than 500°C is not preferable because sintering of the barrier rib pattern does not proceed, and the strength of the barrier rib obtained decreases. The firing temperature being higher than 650°C is not preferable because the bottom of the pattern is thickened due to softening of the barrier rib glass, so that Lb/Lh easily becomes greater than 3. By the step described above, the organic component is removed from the grid-shaped photosensitive paste coating film pattern, and the low-melting-point glass contained in the coating film pattern is softened and sintered to obtain a barrier rib member in which a grid-like barrier rib substantially composed of an inorganic substance is formed on a substrate.
- For preventing leakage of light from the barrier rib, it is preferable that a reflecting film is formed on a surface of the barrier rib and a substrate surface which is not provided with the barrier rib. The material of the reflecting film is not particularly limited, but use of a material which is pervious to X-rays and reflects visible light, an electromagnetic wave of 300 to 800 nm emitted by the phosphor, is preferable. Particularly, a metal such as Ag, Au, Al, Ni or Ti or a metal oxide, which is less degradable is preferable. In the present invention, the surface of the barrier rib refers to a surface of the barrier rib except for a surface where the barrier rib and the substrate are not in contact with each other, i.e. the top of the barrier rib and the side surface of the barrier rib.
- Formation of the reflecting film after formation of the barrier rib is preferable because reflecting films having the same material can be simultaneously formed on the surface of the barrier rib and the substrate surface which is not provided with the barrier rib. As a result, reflecting films having similar reflectivities can be formed on the side surface of the barrier rib and the substrate surface, so that visible light emitted by the phosphor can be uniformly guided to the sensor side more efficiently. It is preferable that a reflecting film is not formed on the substrate surface before formation of the barrier rib. In other words, it is preferable that a deflecting film is not formed on the surface where the barrier rib and the substrate are in contact with each other. This is because in the step of exposing the barrier rib, exposure light is scattered by the reflecting film, so that a high-definition pattern cannot be formed.
- The method for forming a reflecting film is not particularly limited, and various kinds of film formation methods can be used such as a method in which a reflecting material is made pasty, applied to the surface, and then fired to remove a solvent, and a method in which a reflecting material is injected by a spray. Particularly, a vacuum film formation method such as vacuum deposition, sputtering, ion plating, CVD or laser ablation is preferable because a uniform reflecting film can be formed at a lower temperature, and sputtering is more preferable because a uniform film can be formed on the side surface of the barrier rib. If a temperature higher than the firing temperature of the barrier rib is applied during formation of the reflecting film, the barrier rib is deformed, and therefore the temperature during formation of the reflecting film is preferably lower than the temperature during formation of the barrier rib.
- Next, a phosphor is filled in cells divided by the barrier rib, whereby a scintillator panel can be completed. Here, the cell refers to a space divided by a grid-like barrier rib. The phosphor filled in the cell is referred to as a scintillator layer.
- For the phosphor, various known phosphor materials can be used. Particularly, a material having a high conversion rate of an X-ray to visible light, such as CsI, Gd2O2S Lu2O2S Y2O2S, LaCl3, LaBr3, LaI3, CeBr3, CeI3, LuSiO5 or Ba (Br, F, Zn), is used, but the phosphor is not limited thereto. For enhancing luminous efficiency, various kinds of activators may be added. For example, in the case of CsI, a mixture of CsI and sodium iodide (NaI) in an arbitrary molar ratio, or CsI containing activation substances such as indium (In), thallium (Tl), lithium (Li), potassium (K), rubidium (Rb) or sodium (Na) is preferable. Further, a thallium compound such as thallium bromide (TlBr), thallium chloride (TlCl) or thallium fluoride (TlF, TlF3) can also be'used as an activator.
- For formation of a scintillator layer, for example, a method in which crystalline CsI is deposited by vacuum deposition (in this case, it is also possible to co-deposit a thallium compound such as thallium bromide) ; a method in which a slurry of a phosphor dispersed in water is applied to a substrate; or a method in which a phosphor paste prepared by mixing a phosphor powder, an organic binder such as ethyl cellulose or an acrylic resin, and an organic solvent such as terpineol or γ-butyrolactone is applied using screen printing or a dispenser, can be used.
- The amount of the phosphor filled in cells divided by the barrier rib is preferably 50% to 100% in terms of a volume fraction of the phosphor. The volume fraction of the phosphor in cells is referred to as a phosphor filling ratio. If the phosphor filling ratio is less than 50%, efficiency with which incident X-rays are converted to visible light is low. For enhancing conversion efficiency of incident X-rays, efficiency of conversion into visible light can be enhanced by increasing the aspect ratio of the barrier rib height to the barrier rib pitch, but it is preferable to fill the' phosphor in the space of the cell with a high density because efficiency can be further enhanced.
- For preventing reflectance and transmission of light, it is preferable to form a light shielding film between the barrier rib and the reflecting film. The material of the light shielding film is not particularly limited, and a metal film of chromium, nichrome, tantalum or the like, a resin containing a black pigment such as carbon, or the like can be used. The method for forming a light shielding film is not particularly limited, and a method including applying a pasty material, or various kinds of vacuum film formation methods can be used.
- The present invention will be described in detail below by way of Examples. However, the present invention is not limited thereto.
- Raw materials used for the barrier rib photosensitive paste of Examples are as follows.
- Photosensitive polymer: product of addition reaction of 0.4 equivalents of glycidyl methacrylate to carboxyl groups of a copolymer of methacrylic acid/methyl methacrylate/styrene in a mass ratio of 40/40/30 (weight average molecular weight: 43000, acid value: 100)
Photo-polymerization initiator: - 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 ("IC369" manufactured by BASF)
- Ultraviolet ray absorber solution: 0.3 mass% γ-butyrolactone solution of Sudan IV (manufactured by TOKYO OHKA KOGYO Co., Ltd.)
- 1,6-hexanediol-bis[(3,5-di-t-butyl-4-hydroxyphenyl)propiona te])
- Viscosity modifier: Flownon EC121 (manufactured by KYOEISHA CHEMICAL CO., LTD.)
- Organic solvent: γ-butyrolactone
- 27% by mass of SiO2, 31% by mass of B2O3, 6% by mass of ZnO, 7% by mass of Li2O, 2% by mass of MgO, 2% by mass of CaO, 2% by mass of BaO, 23% by mass of Al2O3, refractive index (ng) : 1. 560, glass softening temperature: 588°C, thermal expansion coefficient: 70 x 10-7, average particle diameter: 2.3 µm Low-melting-point glass powder B:
- 28% by mass of SiO2, 30% by mass of B2O3, 6% by mass of ZnO, 2% by mass of Li2O, 3% by mass of MgO, 3% by mass of CaO, 3% by mass of BaO, 25% by mass of Al2O3, refractive index (ng) : 1. 551, glass softening temperature: 649°C, thermal expansion coefficient: 49 x 10-7, average particle diameter: 2.1 µm Low-melting-point glass powder C:
- 30% by mass of SiO2, 34% by mass of B2O3, 4% by mass of ZnO, 1% by mass of Li2O, 1% by mass of MgO, 2% by mass of CaO, 3% by mass of BaO, 26% by mass of Al2O3, refractive index (ng) : 1.542, glass softening temperature: 721°C, thermal expansion coefficient: 38 x 10-7, average particle diameter: 2.0 µm Low-melting-point glass powder D:
- 22% by mass of SiO2, 30% by mass of B2O3, 1% by mass of ZnO, 8% by mass of Li2O, 10% by mass of Na2O, 6% by mass of K2O, 4% by mass of MgO, 11% by mass of BaO, 8% by mass of Al2O3, refractive index (ng) : 1.589, glass softening temperature: 520°C, thermal expansion coefficient: 89 x 10-7, average particle diameter: 2.4 µm
- 30% by mass of SiO2, 31% by mass of B2O3, 6% by mass of ZnO, 2% by mass of MgO, 2% by mass of CaO, 2% by mass of BaO, 27% by mass of Al2O3, refractive index (ng): 1.55, softening temperature: 790°C, thermal expansion coefficient: 32 x 10-7, average particle diameter: 2.3 µm
- An organic solution having the composition shown in Table 1 was prepared. The compositions shown in Table 1 are all based on parts by mass.. 10 parts by mass of a photosensitive monomer, 24 parts by mass of a photosensitive polymer, 6 parts by mass of a photo-polymerization initiator, 0.2 part by mass of a polymerization inhibitor and 12.8 parts by mass of an ultraviolet ray absorber solution were dissolved in 38 parts by mass of an organic solvent under heating at a temperature of 80°C. After the obtained solution was cooled, 9 parts by mass of a viscosity modifier was added to prepare an
organic solution 1. The refractive index (ng) of an organic coating film obtained by applying theorganic solution 1 to a glass substrate and drying the applied solution was 1.553. - Next, to 60 parts by mass of the
organic solution 1 were added 50 parts by mass of the low-melting-point glass powder A and 10 parts by mass of the high-melting-point glass powder E, followed by kneading the mixture by a three-roll kneader to prepare a barrier rib photosensitive paste A. - The barrier rib photosensitive paste A was applied to a glass substrate of 500 mm x 500 mm ("OA-10" manufactured by NIPPON ELECTRIC GLASS Co., Ltd.) by a die coater so as to have a dry thickness of 580 µm, and dried to form a barrier rib photosensitive paste coating film. Next, the barrier rib photosensitive paste coating film was exposed at 700 mJ/cm2 by an ultra-high pressure mercury lamp through a photomask (chrome mask) having a grid-like opening corresponding to a barrier rib pattern and having pitch of 160 µm. The exposed barrier rib photosensitive paste coating film was developed in a 0.5% aqueous ethanolamine solution, so that an unexposed part was removed to form a grid-like photosensitive paste coating film pattern. Further, the photosensitive paste coating film pattern was fired in air at 585°C for 15 minutes to remove organic components and soften and sinter the low-melting-point glass, thereby obtaining a grid-like barrier rib.
- Thereafter, an oxysulfide gadolinium having a particle diameter of 5 µm was mixed with ethyl cellulose, and the mixture was then filled in cells divided by the grid-like barrier rib, and was fired at 450°C to form a scintillator layer having a phosphor filling ratio of 90%, thereby preparing a
scintillator panel 1. - The shape of the cross section of the formed barrier rib was observed with a scanning electron microscope. In the case of a shape as shown in
Fig. 1, 2 ,3 or5 , Lt, Lh and Lb were calculated. When it was difficult to measure Lt or Lb as inFig. 2 or6 , L90 in place of Lt or L10 in place of Lb was measured. Measurement results are shown in Table 4. The shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Example 1 was similar to that inFig. 3 . - The obtained
scintillator panel 1 was evaluated for (1) peeling or breakage of the barrier rib and (2) coating uniformity of the phosphor. Evaluation results are shown in Table 4. A sample free from defects for all the evaluation items was rated good. In Example 1, good results were obtained with the barrier rib and phosphor being free from defects. - Next, a photoelectric conversion element including a PIN type photodiode and a TFT and having a pixel size of 160 µm x 160 µm was disposed on a glass substrate in a matrix form, and a wiring portion including a bias wiring for applying a bias to the PIN type photodiode, a driving wiring for applying a driving signal to the TFT, a signal wiring for outputting a signal charge transferred by the TFT, and so on was formed to prepare an output substrate. The output substrate and the
scintillator panel 1 were bonded to each other with a adhesive, which contained a hot melt resin and had a thickness of 10 µm, interposed therebetween so that the photoelectric converter and the scintillator layer faced each other, thereby completing an X-ray detector. - For the prepared X-ray detector, X-rays at a tube voltage of 80 kVp were applied from the substrate side of the scintillator panel to photograph a solid image, and the photograph was observed to evaluate light emitting characteristics. Evaluation results are shown in Table 4. A sample free from image defects such as crosstalk or pixel defects, and luminance reduction or unevenness was rated good. In Example 1, images, which were free from image defects and had a high luminance and a high definition, were obtained.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, and the exposure amount in the exposure step was changed to 1000 mJ/cm2. The prepared scintillator panel and X-ray. detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as' shown in Table 1, and the exposure amount in the exposure step was changed to 1000 mJ/cm2. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the dry thickness of the barrier rib photosensitive paste coating film was changed to 350 µm, the exposure amount in the exposure step was changed to 630 mJ/cm2, and the pitch of the photomask and the photoelectric conversion element was 80 µm. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 4 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the exposure amount in the exposure step was changed to 900 mJ/cm2, and the barrier rib firing temperature was changed to 595°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 4 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the exposure amount in the exposure step was changed to 520 mJ/cm2, and the barrier rib firing temperature was changed to 595°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 1000 µm, the exposure amount in the exposure step was changed to 1100 mJ/cm2, and the pitch of the photomask and the photoelectric conversion element was changed to 210 µm. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 7 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 1, and the exposure amount in the exposure step was changed to 900 mJ/cm2. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 4.
[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Photosensitive monomer 10 10 10 10 10 10 10 10 Photosensitive polymer 24 24 24 24 24 24 24 24 Photopolymerization initiator 6 3 1.5 6 6 6 6 3 Ultraviolet ray absorber solution 12.8 6.4 9.6 9.6 9.6 9.6 12.8 6.4 Organic solvent 38 38 38 38 38 38 38 38 Polymerization inhibitor 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Viscosity modifier 9 9 9 9 9 9 9 9 - A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 7 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 920 mJ/cm2. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 1100 mJ/cm2. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, and the exposure amount in the exposure step was changed to 1000 mJ/cm2. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 630 µm, the exposure amount in the exposure step was changed to 850 mJ/cm2, and the barrier rib firing temperature was changed to 650°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 255 µm, the exposure amount in the exposure step was changed to 690 mJ/cm2, and the barrier rib firing temperature was changed to 650°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 360 µm, the exposure amount in the exposure step was changed to 550 mJ/cm2, the barrier rib firing temperature was changed to 635°C, and the pitch of the photomask and the photoelectric conversion element was changed to 80 µm. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 2, the low-melting-point glass powder A was changed to the low-melting-point glass powder B, the exposure amount in the exposure step was changed to 900 mJ/cm2, the barrier rib firing temperature was changed to 635°C, and the pitch of the photomask and the photoelectric conversion element was changed to 80 µm. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 5.
[Table 2] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Photosensitive monomer 10 20 8 10 10 10 10 Photosensitive polymer 24 24 24 23 23 23 23 Photopolymerization initiator 1.5 1.5 1.5 6 6 6 6 Ultraviolet ray absorber solution 9.6 9.6 9.6 12.8 12.8 9.6 9.6 Organic solvent 38 38 38 39 39 39 39 Polymerization inhibitor 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Viscosity modifier 9 9 9 9 9 9 9 - A barrier rib was prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, and the low-melting-point glass powder A was changed to the low-melting-point glass powder C. The prepared barrier rib was evaluated in the same manner as in the case of the
scintillator panel 1. Evaluation results are shown in Table 6. When the refractive index of the low-melting-point glass as a raw material of the barrier rib photosensitive paste is low, exposure light does not reach the bottom of the barrier rib. Accordingly, the shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Comparative Example 1 was similar to that in the schematic view ofFig. 5 , so that a large number of peelings, breakages and torsions occurred in the barrier rib. - A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the low-melting-point glass powder A was changed to the low-melting-point glass powder C, the exposure amount in the exposure step was changed to 1000 mJ/cm2, and the barrier rib firing temperature was changed to 650°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. Exposure light reached the bottom of the barrier rib, but the shape of the cross section perpendicular to the longitudinal direction in the barrier rib of Comparative Example 2 was similar to that in the schematic view of
Fig. 6 , so that a large number of breakages of the barrier rib and protrusions with the phosphor flowing out from cells occurred. For light emitting characteristics, luminance unevenness and considerable luminance reduction occurred. - A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the dry film thickness of the barrier rib photosensitive paste coating film was changed to 1000 µm, the exposure amount in the exposure step was changed to 2000 mJ/cm2, and the pitch of the photomask and the photoelectric conversion element was changed to 210 µm. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. The bottom of the barrier rib was significantly thick, and considerable luminance reduction occurred.
- A scintillator panel and an X-ray detector were prepared by performing the same operations as in Example 1 except that the composition of the organic solution in the step of producing a barrier rib photosensitive paste was changed as shown in Table 3, the low-melting-point glass powder A was changed to the low-melting-point glass powder D, and the firing temperature was changed to 530°C. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. The height of the barrier rib was low, the bottom of the barrier rib was significantly thick, and considerable luminance reduction occurred due to coating failure of the phosphor.
[Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Photosensitive monomer 10 10 10 ' 10 Photosensitive polymer 24 24 24 24 Photopolymerization initiator 6 3 6 6 Ultraviolet ray absorber solution 12.8 6.4 3.2 12.8 Organic solvent 38 38 38 38 Polymerization inhibitor 0.2 0.2 0.2 0.2 Viscosity modifier 9 9 9 9 - 50 parts by mass of a terpineol solution containing 10% by mass of ethyl cellulose and 50 parts by mass of the low-melting-point glass powder A were mixed to prepare a screen printing paste. The refractive index (ng) of an organic coating film obtained by applying a terpineol solution, which contained 10% by mass of ethyl cellulose, to a glass substrate and drying the applied solution was 1.49. The printing paste was repeatedly applied in a film thickness of 40 µm by screen printing and dried for 12 layers using a pattern having pitches of 160 µm in longitudinal and traverse directions, an opening length of 125 µm x 125 µm, a wall width of 35 µm and a size appropriate to a predetermined number of pixels. Thereafter, firing was performed in air at 550°C to prepare a barrier rib. Thereafter, a scintillator panel and an X-ray detector were prepared by performing the operations as in Example 1. The prepared scintillator panel and X-ray detector were evaluated in the same manner as in Example 1. Evaluation results are shown in Table 6. A large number of torsions of the barrier rib and coating failures of the phosphor occurred.
[Table 4] Example 1 Example 2* Example 3* Example 4 Example 5 Example 6 Example 7 Example 8 Similar cross section shape Fig. 3 Fig. 2 Fig. 2 Fig. 1 Fig. 4 Fig. 4 Fig. 3 Fig. 3 Lt [µm] 25 21 25 15 22 5 32 35 Lh [µm] 27 25 30 20 24 9 32 42 Lb [µm] 38 39 43 22 42 26 46 55 Lt/Lh 0.93 0.84 0.83 0.75 0.92 0.56 1 0.83 Lb/Lh 1.41 1.56 1.43 1.1 1.75 2.89 1.44 1.31 R [µm] - - - - 14 9 - - H [µm] 400 350 410 250 220 230 700 710 P [µm] 160 160 160 80 80 80 210' 210 Barrier rib defects Good Good Good Good Good Good Good Good Phosphor defects Good Good Good Good Good Good Good Good Light emitting characteristics Good Good Good Good Good Good Good Good * L90 in place of Lt and L10 in place of Lb is shown. [Table 5] Example 9 Example 10 Example 11 Example 12* Example 13* Example 14 Example 15* Similar cross section shape Fig. 3 Fig. 1 Fig. 3 Fig. 2 Fig. 2 Fig. 1 Fig. 2 Lt [µm] 38 27 13 28 12 4 22 Lh [µm] 45 32 29 32 15 7 30 Lb [µm] 61 50 45 66 33 10 56 Lt/Lh 0.84 0.84 0.45 0.88 0.8 0.57 0.73 Lb/Lh 1.36 1.56 1.55 2.06 2.2 1.43 1.87 R [µm] - - - - - - - H [µm] 720 430 400 500 200 250 450 P [µm] 210 160 160 160 160 80 80 Barrier rib defects Good Good Good Good Good Good Good Phosphor defects Good Good Good Good Good Good Good Light emitting characteristics Good Good Good Good Good Good Good * L90 in place of Lt and L10 in place of Lb is shown. [Table 6] Comparative Example 1 Comparative Example 2* Comparative Example 3 Comparative Example 4* Comparative Example 5 Similar cross section shape Fig. 5 Fig. 6 Fig. 3 Fig. 2 - Lt [µm] 30 59 42 12 38 Lh [µm] 27 43 43 32 36 Lb [µm] 25 72 134 120 39 Lt/Lh 1.11 1.37 0.98 0.38 1.06 Lb/Lh 0.93 1.67 3.12 3.75 1.08 R [µm] - - - - - H [µm] 400 400 700 350 400 P [µm] 160 160 210 160 160 Barrier rib defects large number of breakages Breakage Good Good Torsion Phosphor defects Coating impossible Coating unevenness Good Coating failure Coating failure Light emitting characteristics - Luminance unevenness and reduction Luminance reduction Luminance reduction Luminance unevenness * L90 in place of Lt and L10 in place of Lb is shown. - From the above evaluation results, it is apparent that the scintillator panel of the present invention is provided with a barrier rib, which has high luminous efficiency and is free from distortion and the like, in a large area and with high accuracy, and can provide sharp images having reduced image unevenness and linear noises.
-
- 1
- Radiation detector
- 2
- Scintillator panel
- 3
- Output substrate
- 4
- Substrate
- 5
- Buffer layer
- 6
- Barrier rib
- 7
- Scintillator layer
- 8
- Diaphragm layer
- 9
- Photoelectric conversion layer
- 10
- Output layer
- 11
- Substrate
- 12
- Power supply portion
- 13
- Reflecting film
- The present invention can be suitably used as a scintillator panel which constitutes a radiation detector that is used for a medical diagnostic apparatus, a nondestructive inspection instrument and the like.
Claims (6)
- A scintillator panel comprising: a plate-like substrate; a barrier rib provided on the substrate; and a scintillator layer comprising a phosphor filled in cells divided by the barrier rib, wherein
the barrier rib is formed of a material which is mainly
composed of a low-melting-point glass containing 2 to 20% by mass of an alkali metal oxide,
a value obtained by dividing a top width Lt of the barrier rib or a 90%-height width L90 of the barrier rib by a half-value width Lh of the barrier'rib is 0.45 to 1, and
a value obtained by dividing a bottom width Lb of the barrier rib or a 10%-height width L10 of the barrier rib by the half-value width Lh is 1 to 3. - The scintillator panel according to claim 1, wherein the pitch P of the barrier rib is 50 to 120 µm, the half-value width Lh is 5 to 30 µm, and the height H of the barrier rib is 100 to 500 µm.
- The scintillator panel according to claim 1, wherein the pitch P of the barrier rib is 120 to 240 µm, the half-value width Lh is 10 to 40 µm, and the height H of the barrier rib is 200 to 800 µm.
- The scintillator panel according to any one of claims 1 to 3, wherein a line that connects the end of the central portion of the barrier rib to the end of the bottom surface of the barrier rib at a cross section perpendicular to the longitudinal direction in the barrier rib is a curved line.
- The scintillator panel according to any one of claims 1 to 4, wherein a reflecting film is formed on a surface of the barrier rib.
- A method for manufacturing the scintillator panel according to any one of claims 1 to 5, the method comprising:a step of forming a photosensitive paste coating film by applying onto a substrate a photosensitive paste which contains a low-melting-point glass and a photosensitive organic component;an exposure step of exposing the obtained photosensitive paste coating film to light in a predetermined pattern;a development step of dissolving and removing a part of the exposed photosensitive paste coating film which is soluble in a developer;a firing step of heating the photosensitive paste coating film pattern after development to a firing temperature of 500°C to 700°C to remove the organic component and soften and sinter the low-melting-point glass and thereby forming a barrier rib; anda step of filling a phosphor.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012221019 | 2012-10-03 | ||
PCT/JP2013/075156 WO2014054422A1 (en) | 2012-10-03 | 2013-09-18 | Scintillator panel and method for producing scintillator panel |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2905786A1 true EP2905786A1 (en) | 2015-08-12 |
EP2905786A4 EP2905786A4 (en) | 2016-06-15 |
EP2905786B1 EP2905786B1 (en) | 2019-07-10 |
Family
ID=50434752
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13843088.9A Active EP2905786B1 (en) | 2012-10-03 | 2013-09-18 | Scintillator panel and method for producing scintillator panel |
Country Status (7)
Country | Link |
---|---|
US (1) | US9684082B2 (en) |
EP (1) | EP2905786B1 (en) |
JP (1) | JP5488773B1 (en) |
KR (1) | KR101922456B1 (en) |
CN (1) | CN104685575B (en) |
TW (1) | TWI589912B (en) |
WO (1) | WO2014054422A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2916145A4 (en) * | 2012-11-01 | 2016-07-13 | Toray Industries | Radiation detection device and manufacturing method therefor |
EP2924691A4 (en) * | 2012-11-26 | 2016-08-03 | Toray Industries | Scintillator panel and method for producing scintillator panel |
WO2017111681A1 (en) | 2015-12-22 | 2017-06-29 | Scint-X Ab | A scintillator, scintillator assembly, x-ray detector and x-ray imaging system and a method for manufacturing a scintillator |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9564253B2 (en) | 2012-11-16 | 2017-02-07 | Toray Industries, Inc. | Scintillator panel |
EP2924692B1 (en) | 2012-11-26 | 2021-02-17 | Toray Industries, Inc. | Scintillator panel and method for producing same |
JP6221352B2 (en) * | 2013-05-30 | 2017-11-01 | コニカミノルタ株式会社 | Radiation image conversion panel and radiation image detector |
US10042060B2 (en) * | 2014-05-30 | 2018-08-07 | Toray Industries, Inc. | Scintillator panel, radiographic image detection device, and method for manufacturing same |
US9857482B2 (en) * | 2014-07-07 | 2018-01-02 | Toray Industries, Inc. | Scintillator panel, radiation detector, and manufacturing method therefor |
JP6671839B2 (en) * | 2014-10-07 | 2020-03-25 | キヤノン株式会社 | Radiation imaging apparatus and imaging system |
US10145963B2 (en) | 2015-02-12 | 2018-12-04 | National University Corporation Hokkaido University | Scintillator and radiation dosimeter using same |
CN114613790A (en) * | 2020-12-09 | 2022-06-10 | 京东方科技集团股份有限公司 | Scintillator film layer and preparation method thereof, flat panel detector and detection device |
EP4270062A1 (en) | 2020-12-25 | 2023-11-01 | Toray Industries, Inc. | Scintillator panel, radiation detector, radiation inspection device, and method for producing scintillator panel |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5567700A (en) * | 1978-11-16 | 1980-05-21 | Canon Kk | X rayyvisible ray converter * and manufacture therefor |
JPH0560871A (en) | 1991-09-04 | 1993-03-12 | Hamamatsu Photonics Kk | Radiation detection element |
JPH05188148A (en) | 1992-01-13 | 1993-07-30 | Hamamatsu Photonics Kk | Radiation detecting element |
TW375759B (en) * | 1996-07-10 | 1999-12-01 | Toray Industries | Plasma display and preparation thereof |
JP3956889B2 (en) * | 1996-07-10 | 2007-08-08 | 東レ株式会社 | Plasma display |
US20100127180A1 (en) * | 2008-11-24 | 2010-05-27 | Cmt Medical Technologies Ltd. | Scintillator array and a method of constructing the same |
JP2011007552A (en) | 2009-06-24 | 2011-01-13 | Konica Minolta Medical & Graphic Inc | Scintillator panel, radiation detection device, and method of manufacturing the scintillator panel |
JP2011021924A (en) * | 2009-07-14 | 2011-02-03 | Konica Minolta Medical & Graphic Inc | Scintillator panel, radiation detection device, and method of manufacturing scintillator panel |
WO2011111551A1 (en) * | 2010-03-12 | 2011-09-15 | コニカミノルタエムジー株式会社 | Scintillator |
JP2012002627A (en) * | 2010-06-16 | 2012-01-05 | Konica Minolta Medical & Graphic Inc | Two-dimensional array scintillator for radiation detection |
WO2012037148A1 (en) | 2010-09-13 | 2012-03-22 | Parttec, Ltd. | Radiation detector having a ribbed scintillator |
JP2012058170A (en) * | 2010-09-13 | 2012-03-22 | Konica Minolta Medical & Graphic Inc | Scintillator panel |
KR101925823B1 (en) | 2011-05-26 | 2018-12-06 | 도레이 카부시키가이샤 | Scintillator panel and method for manufacturing scintillator panel |
-
2013
- 2013-09-18 JP JP2013544595A patent/JP5488773B1/en active Active
- 2013-09-18 US US14/432,300 patent/US9684082B2/en active Active
- 2013-09-18 EP EP13843088.9A patent/EP2905786B1/en active Active
- 2013-09-18 KR KR1020157005451A patent/KR101922456B1/en active IP Right Grant
- 2013-09-18 WO PCT/JP2013/075156 patent/WO2014054422A1/en active Application Filing
- 2013-09-18 CN CN201380051929.0A patent/CN104685575B/en active Active
- 2013-10-02 TW TW102135613A patent/TWI589912B/en active
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2916145A4 (en) * | 2012-11-01 | 2016-07-13 | Toray Industries | Radiation detection device and manufacturing method therefor |
EP2924691A4 (en) * | 2012-11-26 | 2016-08-03 | Toray Industries | Scintillator panel and method for producing scintillator panel |
US9791576B2 (en) | 2012-11-26 | 2017-10-17 | Toray Industries, Inc. | Scintillator panel and method for manufacturing scintillator panel |
WO2017111681A1 (en) | 2015-12-22 | 2017-06-29 | Scint-X Ab | A scintillator, scintillator assembly, x-ray detector and x-ray imaging system and a method for manufacturing a scintillator |
EP3394641A4 (en) * | 2015-12-22 | 2019-08-14 | Scint-X AB | A scintillator, scintillator assembly, x-ray detector and x-ray imaging system and a method for manufacturing a scintillator |
Also Published As
Publication number | Publication date |
---|---|
KR101922456B1 (en) | 2018-11-27 |
JPWO2014054422A1 (en) | 2016-08-25 |
US9684082B2 (en) | 2017-06-20 |
EP2905786B1 (en) | 2019-07-10 |
US20150241569A1 (en) | 2015-08-27 |
WO2014054422A1 (en) | 2014-04-10 |
KR20150066516A (en) | 2015-06-16 |
CN104685575B (en) | 2017-05-24 |
JP5488773B1 (en) | 2014-05-14 |
CN104685575A (en) | 2015-06-03 |
TWI589912B (en) | 2017-07-01 |
EP2905786A4 (en) | 2016-06-15 |
TW201418754A (en) | 2014-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2905786B1 (en) | Scintillator panel and method for producing scintillator panel | |
US9632185B2 (en) | Scintillator panel and method for manufacturing the same | |
EP2717272B1 (en) | Scintillator panel and method for manufacturing scintillator panel | |
EP2922067B1 (en) | Scintillator panel | |
EP2916145A1 (en) | Radiation detection device and manufacturing method therefor | |
WO2014021415A1 (en) | Scintillator panel and method for producing scintillator panel | |
US9791576B2 (en) | Scintillator panel and method for manufacturing scintillator panel | |
JP6075028B2 (en) | Scintillator panel | |
JP2014106022A (en) | Scintillator panel | |
JP6217076B2 (en) | Scintillator panel and method for manufacturing scintillator panel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20150204 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
RA4 | Supplementary search report drawn up and despatched (corrected) |
Effective date: 20160512 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: G01T 1/20 20060101ALI20160506BHEP Ipc: G21K 4/00 20060101AFI20160506BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: IGUCHI, YUICHIRO Inventor name: KINOSHITA, HIDEKI Inventor name: OKAMURA, MASAKI |
|
INTG | Intention to grant announced |
Effective date: 20190211 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1154410 Country of ref document: AT Kind code of ref document: T Effective date: 20190715 Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013057742 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1154410 Country of ref document: AT Kind code of ref document: T Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191010 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191111 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191010 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191011 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191110 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200224 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013057742 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG2D | Information on lapse in contracting state deleted |
Ref country code: IS |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190918 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190918 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190930 |
|
26N | No opposition filed |
Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20191010 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20191010 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20130918 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190710 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230515 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20230816 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230808 Year of fee payment: 11 Ref country code: DE Payment date: 20230802 Year of fee payment: 11 |